Benzotriazol-1-yl-aminoacetonitrile compounds and their use in the control of parasite disease

ABSTRACT

The invention relates to benzotriazol-1-yl-aminoacetonitrile compounds and optionally the enantiomers thereof. The active ingredients have advantageous pesticidal properties. They are especially suitable for controlling parasites on warm-blooded animals.

This application is a National Phase Application under § 371 ofInternational Application Number PCT/EP03/10047 filed on Sep. 10, 2003.

The present invention relates to new benzotriazolyl-aminoacetonitrilecompounds of formula

wherein

-   R₃, R₄ and R₅ either, independently of one another, signify    hydrogen, halogen, C₁–C₆-alkyl, halo-C₁–C₆-alkyl; C₃–C₆-cycloalkyl    that is either unsubstituted or substituted once or many times,    whereby the substituents may be independent of one another and are    selected from the group consisting of halogen and C₁–C₆-alkyl;    phenyl that is either unsubstituted or substituted once or many    times, whereby the substituents may be independent of one another    and are selected from the group consisting of halogen, nitro, cyano,    C₁–C₆-alkyl, halo-C₁–C₆-alkyl, C₁–C₆-alkoxy, halo-C₁–C₆-alkoxy,    C₁–C₆-alkylthio, halo-C₁–C₆-alkylthio, C₁–C₆-alkylsulfinyl,    halo-C₁–C₆-alkylsulfinyl, C₁–C₆-alkylsulfonyl,    halo-C₁–C₆-alkylsulfonyl, C₁–C₆-alkylamino or di-(C₁–C₆-alkyl)amino;-   R₃, R₄ and R₅ either, independently of one another, signify    hydrogen, halogen, C₁–C₆-alkyl, halo-C₁–C₆-alkyl; C₃–C₆-cycloalkyl    that is either unsubstituted or substituted once or many times,    whereby the substituents may be independent of one another and are    selected from the group consisting of halogen and C₁–C₆-alkyl;    phenyl that is either unsubstituted or substituted once or many    times, whereby the substituents may be independent of one another    and are selected from the group consisting of halogen, nitro, cyano,    C₁–C₆-alkyl, halo-C₁–C₆-alkyl, C₁–C₆-alkoxy, halo-C₁–C₆-alkoxy,    C₁–C₆-alkylthio, halo-C₁–C₆-alkylthio, C₁–C₆-alkylsulfinyl,    halo-C₁–C₆-alkylsulfinyl, C₁–C₆-alkylsulfonyl,    halo-C₁–C₆-alkylsulfonyl, C₁–C₆-alkylamino or di-(C₁–C₆-alkyl)amino;-   or R₄ and R₅ together signify C₂–C₆-alkylene;-   R₆ signifies hydrogen, C₁–C₆-alkyl, C₁–C₆-alkylcarbonyl,    C₁–C₆-alkoxy-C₁–C₆-alkyl, aminocarbonyl, C₁–C₆-alkoxycarbonyl,    halo-C₁–C₆-alkylcarbonyl, thio-C₁–C₆-alkylcarbonyl or benzyl;-   R₇ signifies hydrogen, C₁–C₆-alkyl, C₁–C₆-alkoxy, C₁–C₆-alkylamino,    di(C₁–C₆-alkyl)amino, piperonyl, phenyl which is unsubstituted or    substituted once or many times, whereby the substituents may be    independent of one another and are selected from the group    consisting of halogen, nitro, cyano, C₁–C₆-alkyl, C₃–C₆-cycloalkyl,    halo-C₁–C₆-alkyl, C₁–C₆-alkoxy, C₃–C₆-cycloalkyloxy,    halo-C₁–C₆-alkoxy, C₂–C₆-alkenyl, halo-C₂–C₆-alkenyl, C₂–C₆-alkinyl,    C₃–C₆-cycloalkyl, C₂–C₆-alkenyloxy, halo-C₂–C₆-alkenyloxy,    C₁–C₆-alkylthio, halo-C₁–C₆-alkylthio, C₁–C₆-alkylsulfonyloxy,    halo-C₁–C₆-alkylsulfonyloxy, C₁–C₆-alkylsulfinyl,    halo-C₁–C₆-alkylsulfinyl, C₁–C₆-alkylsulfonyl,    halo-C₁–C₆-alkylsulfonyl, C₂–C₆-alkenylthio, halo-C₂–C₆-alkenylthio,    C₂–C₆-alkenylsulfinyl, halo-C₂–C₆-alkenylsulfinyl,    C₂–C₆-alkenylsulfonyl, halo-C₂–C₆-alkenylsulfonyl, C₁–C₆-alkylamino,    di(C₁–C₆-alkyl)amino, C₁–C₆-alkylsulfonylamino,    halo-C₁–C₆-alkylsulfonylamino, C₁–C₆-alkylcarbonyl,    halo-C₁–C₆-alkylcarbonyl, C₁–C₆-alkoxycarbonyl,    C₁–C₆-alkylaminocarbonyl, di(C₁–C₆-alkyl)aminocarbonyl;    aryl-C₁–C₆-alkyl which is unsubstituted or substituted once or many    times, arylamino which is unsubstituted or substituted once or many    times, arylcarbonyl which is unsubstituted or substituted once or    many times, arylcarbonyloxy which is unsubstituted or substituted    once or many times, aryloxy which is unsubstituted or substituted    once or many times, aryloxy-C₁–C₆-alkyl which is unsubstituted or    substituted once or many times, hetaryloxy-C₁–C₆-alkyl which is    unsubstituted or substituted once or many times, aryloxycarbonyl    which is unsubstituted or substituted once or many times,    arylsulfonyl which is unsubstituted or substituted once or many    times, arylsulfonylamino which is unsubstituted or substituted once    or many times, pyridyloxy which is unsubstituted or substituted once    or many times, and phenylacetylenyl which is unsubstituted or    substituted once or many times, whereby the substituents may each be    independent of one another and are selected from the group    consisting of halogen, nitro, cyano, C₁–C₆-alkyl, halo-C₁–C₆-alkyl,    C₁–C₆-alkoxy, halo-C₁–C₆-alkoxy, C₁–C₆-alkylthio,    halo-C₁–C₆-alkylthio, C₁–C₆-alkylsulfinyl, halo-C₁–C₆-alkylsulfinyl,    C₁–C₆-alkylsulfonyl and halo-C₁–C₆-alkylsulfonyl;-   unsubstituted hetaryl or hetaryl which is substituted once or many    times, whereby the substituents may be independent of one another    and are selected from the group consisting of halogen, nitro, cyano,    C₁–C₆-alkyl, halo-C₁–C₆-alkyl, C₀–C₆-alkoxy, halo-C₁–C₆-alkoxy,    C₂–C₆-alkenyloxy, halo-C₂–C₆-alkenyloxy, C₁–C₆-alkylthio,    halo-C₁–C₆-alkylthio, C₁–C₆-alkylsulfinyl, halo-C₁–C₆-alkylsulfinyl,    C₂–C₆-alkenylthio, halo-C₂–C₆-alkenylthio, C₂–C₆-alkenylsulfinyl,    halo-C₂–C₆-alkenylsulfinyl, C₁–C₆-alkylsulfonyl and    halo-C₁–C₆-alkylsulfonyl, C₂–C₆-alkenylsulfonyl,    halo-C₂–C₆-alkenylsulfonyl, C₁–C₆-alkylamino and    di-(C₁–C₆-alkyl)amino;-   or naphthyl or quinolyl which are unsubstituted or substituted once    or many times, whereby the substituents may be independent of one    another and are selected from the group consisting of halogen,    nitro, cyano, C₁–C₆-alkyl, halo-C₁–C₆-alkyl, C₁–C₆-alkoxy,    halo-C₁–C₆-alkoxy, C₂–C₆-alkenyloxy, halo-C₂–C₆-alkenyloxy,    C₁–C₆-alkylthio, halo-C₁–C₆-alkylthio, C₁–C₆-alkylsulfinyl,    halo-C₁–C₆-alkylsulfinyl, C₂–C₆-alkenylthio, halo-C₂–C₆-alkenylthio,    C₂–C₆-alkenylsulfinyl, halo-C₂–C₆-alkenylsulfinyl,    C₁–C₆-alkylsulfonyl, halo-C₁–C₆-alkylsulfonyl,    C₂–C₆-alkenylsulfonyl, halo-C₂–C₆-alkenylsulfonyl, C₁–C₆-alkylamino    and di-(C₁–C₆-alkyl)amino;-   R₈ and R₉, independently of one another, signify hydrogen,    C₁–C₆-alkyl, C₁–C₆-alkoxycarbonyl, C₁–C₆-alkylcarbonyl,    C₁–C₆-alkylthiocarbonyl, thio-C₁–C₆-alkylcarbonyl, aryl or hetaryl;-   Y signifies a direct bond,C(O),C(S) or S(O)_(n);-   a signifies 1, 2 or 3;-   m signifies 0, 1, 2, 3 or 4; and-   n is 1 or 2;    their preparation and use in the control of endo- and ectoparasites,    especially helminths, in and on warm-blooded productive livestock    and domestic animals and plants, and furthermore pesticides    containing at least one of these compounds.

Substituted aminoacetonitrile compounds having pesticidal activity aredescribed for example in EP-0.953.565 A2. However, the activeingredients specifically disclosed therein cannot always fulfill therequirements regarding potency and activity spectrum. There is thereforea need for active ingredients with improved pesticidal properties. Ithas now been found that the aminoacetonitrile compounds of formula Ihave excellent pesticidal properties, especially against endo- andecto-parasites in and on productive livestock and domestic animals andplants.

Aryl is phenyl or naphthyl.

Hetaryl is pyridyl, pyrimidyl, s-triazinyl, 1,2,4-triazinyl, thienyl,furanyl, pyrryl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, oxazolyl,thiadiazolyl, oxadiazolyl, benzothienyl, benzofuranyl, benzothiazolyl,indolyl or indazolyl, preferably pyridyl, pyrimidyl, s-triazinyl or1,2,4-triazinyl, especially pyridyl or pyrimidyl.

Alkyl—as a group per se and as structural element of other groups andcompounds, for example halogen-alkyl, alkoxy, and alkylthio- is, in eachcase with due consideration of the specific number of carbon atoms inthe group or compound in question, either straight-chained, i.e. methyl,ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl,isobutyl, sec.-butyl, tert.-butyl, isopentyl, neopentyl or isohexyl.

Alkenyl—as a group per se and as structural element of other groups andcompounds—is, in each case with due consideration of the specific numberof carbon atoms in the group or compound in question and of theconjugated or isolated double bonds—either straight-chained, e.g. allyl,2-butenyl, 3-pentenyl, 1-hexenyl or 1,3-hexadienyl, or branched, e.g.isopropenyl, isobutenyl, isoprenyl, tert.-pentenyl or isohexenyl.

Alkinyl—as a group per se and as structural element of other groups andcompounds—is, in each case with due consideration of the specific numberof carbon atoms in the group or, compound in question and of theconjugated or isolated double bonds—either straight-chained, e.g.propargyl, 2-butinyl, 3-pentinyl, 1-hexinyl, 1-heptinyl or3-hexen-1-inyl, or branched, e.g. 3-methylbut-1-inyl, 4-ethylpent-1-inylor 4-methylhex-2-inyl.

Cycloalkyl—as a group per se and as structural element of other groupsand compounds such as halocycloalkyl,—is, in each case with dueconsideration of the specific number of carbon atoms in the group orcompound in question, cyclopropyl, cyclobutyl, cyclopentyl orcyclohexyl.

Halogen—as a group per se and as structural element of other groups andcompounds such as haloalkyl, haloalkoxy and haloalkylthio—is fluorine,chlorine, bromine or iodine, especially fluorine, chlorine or bromine,in particular fluorine or chlorine.

Halogen-substituted carbon-containing groups and compounds, such ashaloalkyl, haloalk-oxy or haloalkylthio, may be partially halogenated orperhalogenated, whereby in the case of multiple halogenation, thehalogen substituents may be identical or different. Examples ofhalogen-alkyl—as a group per se and as structural element of othergroups and compounds such as haloalkoxy or haloalkylthio,—are methylwhich is mono- to trisubstituted by fluorine, chlorine and/or bromine,such as CHF₂ or CF₃; ethyl which is mono- to pentasubstituted byfluorine, chlorine and/or bromine, such as CH₂CF₃, CF₂CF₃, CF₂CCl₃,CF₂CHCl₂, CF₂CHF₂, CF₂CFCl₂, CF₂CHBr₂, CF₂CHClF, CF₂CHBrF or CClFCHClF;propyl or isopropyl, mono- to heptasubstituted by fluorine, chlorineand/or bromine, such as CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃ or CH(CF₃)₂;butyl or one of its isomers, mono- to nonasubstituted by fluorine,chlorine and/or bromine, such as CF(CF₃)CHFCF₃ or CH₂(CF₂)₂CF₃; pentylor one of its isomers substituted once to eleven times by fluorine,chlorine and/or bromine, such as CF(CF₃)(CHF)₂CF₃ or CH₂(CF₂)₃CF₃; andhexyl or one of its isomers substituted once to thirteen times byfluorine, chlorine and/or bromine, such as (CH₂)₄CHBrCH₂Br,CF₂(CHF)₄CF₃, CH₂(CF₂)₄CF₃ or C(CF₃)₂(CHF)₂CF₃.

Alkoxy groups preferably have a chain length of 1 to 6 carbon atoms.Alkoxy is for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy,isobutoxy, sec.-butoxy and tert.-butoxy, as well as the isomerspentyloxy and hexyloxy; preferably methoxy and ethoxy. Haloalkoxy groupspreferably have a chain length of 1 to 6 carbon atoms. Haloalkoxy ise.g. fluoromethoxy, difluoromethoxy, trifluoromethoxy,2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy,2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferablydifluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Alkylthio groups preferably have a chain length of 1 to 6 carbon atoms.Alkylthio is for example methylthio, ethylthio, propylthio,isopropylthio, n-butylthio, isobutylthio, sec.-butylthio ortert.-butylthio, preferably methylthio and ethylthio.

Preferred embodiments within the scope of the invention are:

-   (1) A compound of formula I, wherein R₁ signifies halogen, cyano,    nitro, C₁–C₄-alkyl, halo-C₁–C₄-alkyl, C₁–C₄-alkoxy,    halo-C₁–C₄-alkoxy, C₁–C₄-alkylcarbonyl, halo-C₁–C₄-alkylcarbonyl,    C₁–C₄-alkylsulfonyl or unsubstituted or substituted phenoxy, whereby    the substituents may be independent of one another and are selected    from the group consisting of halogen, nitro, cyano, C₁–C₄-alkyl,    halo-C₁–C₄-alkyl, C₁–C₄-alkoxy and halo-C₁–C₄-alkoxy;-   especially halogen, cyano, nitro, C₁–C₂-alkyl, halo-C₁–C₂-alkyl,    C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy or unsubstituted or substituted    phenoxy, whereby the substituents may be independent of one another    and are selected from the group consisting of halogen, C₁–C₄-alkyl,    halo-C₁–C₄-alkyl, C₁–C₄-alkoxy and halo-C₁–C₄-alkoxy;-   most particularly halogen, cyano, nitro, C₁–C₂-alkyl,    halo-C₁–C₂-alkyl, C₁–C₂-alkoxy or halo-C₁–C₂-alkoxy;-   (2) A compound of formula I, wherein R₃, R₄ and R₅ are either,    independently of one another, hydrogen, halogen, C₁–C₄-alkyl,    halo-C₁–C₄-alkyl, C₃–C₆-cycloalkyl; phenyl that is either    unsubstituted or substituted once or many times, whereby the    substituents may be independent of one another and are selected from    the group consisting of halogen, nitro, cyano, C₁–C₄-alkyl,    halo-C₁–C₄-alkyl, C₁–C₄-alkoxy, halo-C₁–C₄-alkoxy; C₁–C₄-alkylthio    and halo-C₁–C₄-alkylthio; or R₄ and R₅ together are C₂–C₆-alkylene;-   especially, independently of one another, hydrogen, halogen,    C₁–C₂-alkyl, halo-C₁–C₂-alkyl or C₃–C₆-cycloalkyl;-   most particularly, independently of one another, hydrogen, methyl or    halomethyl;-   (3) A compound of formula I, wherein R₆ is hydrogen, C₁–C₄-alkyl,    C₁–C₄-alkylcarbonyl, C₁–C₆-alkoxy-C₁–C₆-alkyl or benzyl;-   especially hydrogen, C₁–C₂-alkyl, C₁–C₂-alkylcarbonyl or benzyl;-   most particularly hydrogen or C₁–C₂-alkyl;-   (4) A compound of formula I, wherein R₇ signifies phenyl which is    unsubstituted or substituted once or many times, whereby the    substituents may be independent of one another and are selected from    the group consisting of halogen, nitro, cyano, C₁–C₄-alkyl,    halo-C₁–C₄-alkyl, C₁–C₄-alkoxy, halo-C₁–C₄-alkoxy, C₂–C₄-alkenyl,    halo-C₂–C₄-alkenyl, C₂–C₄-alkinyl, C₃–C₆-cycloalkyl,    C₂–C₄-alkenyloxy, halo-C₂–C₄-alkenyloxy, C₁–C₄-alkylthio,    halo-C₁–C₄-alkylthio, C₁–C₄-alkylsulfonyloxy,    halo-C₁–C₄-alkylsulfonyloxy, C₁–C₄-alkylsulfonyl,    halo-C₁–C₄-alkylsulfonyl, C₂–C₄-alkenylsulfonyl,    halo-C₂–C₄-alkenylsulfonyl, C₁–C₄-alkylamino, di(C₁–C₄-alkyl)amino,    C₁–C₄-alkylcarbonyl, halo-C₁–C₄-alkylcarbonyl, C₁–C₆-alkoxycarbonyl;    aryl-C₁–C₄-alkyl which is unsubstituted or substituted once or many    times, aryloxy which is unsubstituted or substituted once or many    times, aryloxy-C₁–C₄-alkyl which is unsubstituted or substituted    once or many times, hetaryloxy-C₁–C₄-alkyl which is unsubstituted or    substituted once or many times, aryloxycarbonyl which is    unsubstituted or substituted once or many times, arylsulfonyl which    is unsubstituted or substituted once or many times, and pyridyloxy    which is unsubstituted or substituted once or many times, whereby    the substituents may each be independent of one another and are    selected from the group consisting of halogen, nitro, cyano,    C₁–C₄-alkyl, halo-C₁–C₄-alkyl, C₁–C₄-alkoxy, halo-C₁–C₄-alkoxy,    C₁₋₄-alkylthio, halo-C₁₋₄-alkylthio, C₁–C₄-alkylsulfonyl and    halo-C₁–C₄-alkylsulfonyl; hetaryl which is unsubstituted or    substituted once or many times, whereby the substituents may be    independent of one another and are selected from the group    consisting of halogen, nitro, cyano, C₁–C₄-alkyl, halo-C₁–C₄-alkyl,    C₁–C₄-alkoxy, halo-C₁–C₄-alkoxy, C₂–C₄-alkenyloxy,    halo-C₂–C₄-alkenyloxy, C₁–C₄-alkylthio, halo-C₁–C₄-alkylthio,    C₁–C₄-alkylsulfonyl and halo-C₁–C₄-alkylsulfonyl; or-   naphthyl or quinolyl which are unsubstituted or substituted once or    many times, whereby the substituents may be independent of one    another and are selected from the group consisting of halogen,    nitro, cyano, C₁–C₄-alkyl, halo-C₁–C₄-alkyl, C₁–C₄-alkoxy,    halo-C₁–C₄-alkoxy, C₂–C₄-alkenyloxy, halo-C₂–C₄-alkenyloxy,    C₁–C₄-alkylthio, halo-C₁–C₄-alkylthio, C₂–C₄-alkenylthio,    halo-C₂–C₄-alkenylthio, C₁–C₄-alkylsulfonyl and    halo-C₁–C₄-alkylsulfonyl;-   in particular aryl which is unsubstituted or substituted once or    many times, whereby the substituents may be independent of one    another and are selected from the group consisting of halogen,    nitro, cyano, C₁–C₂-alkyl, halo-C₁–C₂-alkyl, C₁–C₂-alkoxy,    halo-C₁–C₂-alkoxy, C₃–C₅-cycloalkyl, C₁–C₂-alkylthio,    halo-C₁–C₂-alkylthio, C₁–C₂-alkylsulfonyl, halo-C₁–C₂-alkylsulfonyl,    C₁–C₂-alkylcarbonyl, halo-C₁–C₂-alkylcarbonyl, C₁–C₂-alkoxycarbonyl;    aryl-C₁–C₂-alkyl which is unsubstituted or substituted once or many    times, aryloxy which is unsubstituted or substituted once or many    times, aryloxy-C₁–C₂-alkyl which is unsubstituted or substituted    once or many times, and pyridyloxy which is unsubstituted or    substituted once or many times, whereby the substituents may be    independent of one another and are selected from the group    consisting of halogen, nitro, cyano, C₁–C₂-alkyl, halo-C₁–C₂-alkyl,    C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy, C₁–C₂-alkylthio,    halo-C₁–C₂-alkylthio, C₁–C₂-alkylsulfonyl and    halo-C₁–C₂-alkylsulfonyl; or-   hetaryl which is unsubstituted or substituted once or many times,    whereby the substituents may be independent of one another and are    selected from the group consisting of halogen, nitro, cyano,    C₁–C₂-alkyl, halo-C₁–C₂-alkyl, C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy,    C₂–C₄-alkenyloxy, halo-C₂–C₄-alkenyloxy, C₁–C₂-alkylthio,    halo-C₁–C₂-alkylthio, C₁–C₂-alkylsulfonyl and    halo-C₁–C₂-alkylsulfonyl;-   most particularly aryl which is unsubstituted or substituted once or    many times, whereby the substituents may be independent of one    another and are selected from the group consisting of halogen,    cyano, C₁–C₂-alkyl, halo-C₁–C₂-alkyl, C₁–C₂-alkoxy,    halo-C₁–C₂-alkoxy, C₃–C₅-cycloalkyl, C₁–C₂-alkylcarbonyl,    halo-C₁–C₂-alkylcarbonyl, C₁–C₂-alkoxycarbonyl; aryl-C₁–C₂-alkyl    which is unsubstituted or substituted once or many times, and    aryloxy-C₁–C₂-alkyl which is unsubstituted or substituted once or    many times, whereby the substituents may each be independent of one    another and are selected from the group consisting of halogen,    cyano, C₁–C₂-alkyl, halo-C₁–C₂-alkyl, C₁–C₂-alkoxy and    halo-C₁–C₂-alkoxy;-   (5) a compound of formula I, wherein R₈ and R₉ independently of one    another, signify hydrogen, C₁–C₆-alkyl, C₁–C₆-alkoxycarbonyl,    C₁–C₆-alkylcarbonyl or aryl;-   especially, independently of one another, hydrogen or C₁–C₄-alkyl;-   most particularly, independently of one another, hydrogen or    C₁–C₂-alkyl;-   (6) A compound of formula I, wherein Y is C(O) or S(O)_(n);-   especially C(O);-   (7) A compound of formula I, wherein a is 1 or 2;-   especially 1;-   (8) A compound of formula I, wherein m is 1, 2 or 3;-   especially 1 or 2;-   (9) A compound of formula I, wherein n is 2;-   (10) A compound of formula I, wherein-   R₁ signifies halogen, cyano, nitro, C₁–C₄-alkyl, halo-C₁–C₄-alkyl,    C₁–C₄-alkoxy, halo-C₁–C₄-alkoxy, C₁–C₄-alkylcarbonyl,    halo-C₁–C₄-alkylcarbonyl, C₁–C₄-alkylsulfonyl or unsubstituted or    substituted phenoxy, whereby the substituents may be independent of    one another and are selected from the group consisting of halogen,    nitro, cyano, C₁–C₄-alkyl, halo-C₁–C₄-alkyl, C₁–C₄-alkoxy and    halo-C₁–C₄-alkoxy;-   R₃, R₄ and R₅, independently of one another, are hydrogen, halogen,    C₁–C₄-alkyl, halo-C₁–C₄-alkyl, C₃–C₆-cycloalkyl; phenyl that is    either unsubstituted or substituted once or many times, whereby the    substituents may be independent of one another and are selected from    the group consisting of halogen, nitro, cyano, C₁–C₄-alkyl,    halo-C₁–C₄-alkyl, C₁–C₄-alkoxy, halo-C₁–C₄-alkoxy; C₁–C₄-alkylthio    and halo-C₁–C₄-alkylthio; or R₄ and R₅ together are C₂–C₆-alkylene;-   R₆ is hydrogen, C₁–C₄-alkyl, C₁–C₄-alkylcarbonyl,    C₁–C₆-alkoxy-C₁–C₆-alkyl or benzyl;-   R₇ signifies phenyl which is unsubstituted or substituted once or    many times, whereby the substituents may be independent of one    another and are selected from the group consisting of halogen,    nitro, cyano, C₁–C₄-alkyl, halo-C₁–C₄-alkyl, C₁–C₄-alkoxy,    halo-C₁–C₄-alkoxy, C₂–C₄-alkenyl, halo-C₂–C₄-alkenyl, C₂–C₄-alkinyl,    C₃–C₆-cycloalkyl, C₂–C₄-alkenyloxy, halo-C₂–C₄-alkenyloxy,    C₁–C₄-alkylthio, halo-C₁–C₄-alkylthio, C₁–C₄-alkylsulfonyloxy,    halo-C₁–C₄-alkylsulfonyloxy, C₁–C₄-alkylsulfonyl,    halo-C₁–C₄-alkylsulfonyl, C₂–C₄-alkenylsulfonyl,    halo-C₂–C₄-alkenylsulfonyl, C₁–C₄-alkylamino, di(C₁–C₄-alkyl)amino,    C₁–C₄-alkylcarbonyl, halo-C₁–C₄-alkylcarbonyl, C₁–C₆-alkoxycarbonyl;    aryl-C₁–C₄-alkyl which is unsubstituted or substituted once or many    times, aryloxy which is unsubstituted or substituted once or many    times, aryloxy-C₁–C₄-alkyl which is unsubstituted or substituted    once or many times, hetaryloxy-C₁–C₄-alkyl which is unsubstituted or    substituted once or many times, aryloxycarbonyl which is    unsubstituted or substituted once or many times, arylsulfonyl which    is unsubstituted or substituted once or many times, and pyridyloxy    which is unsubstituted or substituted once or many times, whereby    the substituents may each be independent of one another and are    selected from the group consisting of halogen, nitro, cyano,    C₁–C₄-alkyl, halo-C₁–C₄-alkyl, C₁–C₄-alkoxy, halo-C₁–C₄-alkoxy,    C₁–C₄-alkylthio, halo-C₁–C₄-alkylthio, C₁–C₄-alkylsulfonyl and    halo-C₁–C₄-alkylsulfonyl;-   hetaryl which is unsubstituted or substituted once or many times,    whereby the substituents may be independent of one another and are    selected from the group consisting of halogen, nitro, cyano,    C₁–C₄-alkyl, halo-C₁–C₄-alkyl, C₁–C₄-alkoxy, halo-C₁–C₄-alkoxy,    C₂–C₄-alkenyloxy, halo-C₂–C₄-alkenyloxy, C₁–C₄-alkylthio,    halo-C₁–C₄-alkylthio, C₁–C₄-alkylsulfonyl and    halo-C₁–C₄-alkylsulfonyl; or-   naphthyl or quinolyl which are unsubstituted or substituted once or    many times, whereby the substituents may be independent of one    another and are selected from the group consisting of halogen,    nitro, cyano, C₁–C₄-alkyl, halo-C₁–C₄-alkyl, C₁–C₄-alkoxy,    halo-C₁–C₄-alkoxy, C₂–C₄-alkenyloxy, halo-C₂–C₄-alkenyloxy,    C₁–C₄-alkylthio, halo-C₁–C₄-alkylthio, C₂–C₄-alkenylthio,    halo-C₂–C₄-alkenylthio, C₁–C₄-alkylsulfonyl and    halo-C₁–C₄-alkylsulfonyl;-   R₈ and R₉ independently of one another, signify hydrogen,    C₁–C₆-alkyl, C₁–C₆-alkoxycarbonyl, C₁–C₆-alkylcarbonyl or aryl;-   Y is C(O) or S(O)_(n);-   a signifies 1 or 2;-   m is 1, 2 or 3 and-   n signifies 2;-   (11) A compound of formula I, wherein-   R₁ signifies halogen, cyano, nitro, C₁–C₂-alkyl, halo-C₁–C₂-alkyl,    C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy or unsubstituted or substituted    phenoxy, whereby the substituents may be independent of one another    and are selected from the group consisting of halogen, C₁–C₄-alkyl,    halo-C₁–C₄-alkyl, C₁–C₄-alkoxy and halo-C₁–C₄-alkoxy;-   R₃, R₄ and R₅, independently of one another, signify hydrogen,    halogen, C₁–C₂-alkyl, halo-C₁–C₂-alkyl or C₃–C₆-cycloalkyl;-   R₆ signifies hydrogen, C₁–C₂-alkyl, C₁–C₂-alkylcarbonyl or benzyl;-   R₇ signifies phenyl which is unsubstituted or substituted once or    many times, whereby the substituents may be independent of one    another and are selected from the group consisting of halogen,    nitro, cyano, C₁–C₂-alkyl, halo-C₁–C₂-alkyl, C₁–C₂-alkoxy,    halo-C₁–C₂-alkoxy, C₃–C₅-cycloalkyl, C₁–C₂-alkylthio,    halo-C₁–C₂-alkylthio, C₁–C₂-alkylsulfonyl, halo-C₁–C₂-alkylsulfonyl,    C₁–C₂-alkylcarbonyl, halo-C₁–C₂-alkylcarbonyl, C₁–C₂-alkoxycarbonyl;    aryl-C₁–C₂-alkyl which is unsubstituted or substituted once or many    times, aryloxy which is unsubstituted or substituted once or many    times, aryloxy-C₁–C₂-alkyl which is unsubstituted or substituted    once or many times, and pyridyloxy which is unsubstituted or    substituted once or many times, whereby the substituents may be    independent of one another and are selected from the group    consisting of halogen, nitro, cyano, C₁–C₂-alkyl, halo-C₁–C₂₇alkyl,    C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy, C₁–C₂-alkylthio,    halo-C₁–C₂-alkylthio, C₁–C₂-alkylsulfonyl and    halo-C₁–C₂-alkylsulfonyl; or-   hetaryl which is unsubstituted or substituted once or many times,    whereby the substituents may be independent of one another and are    selected from the group consisting of halogen, nitro, cyano,    C₁–C₂-alkyl, halo-C₁–C₂-alkyl, C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy,    C₂–C₄-alkenyloxy, halo-C₂–C₄-alkenyloxy, C₁–C₂-alkylthio,    halo-C₁–C₂-alkylthio, C₁–C₂-alkylsulfonyl and    halo-C₁–C₂-alkylsulfonyl;-   R₈ and R₉, independently of one another, signify hydrogen or    C₁–C₄-alkyl;-   Y signifies C(O);-   a signifies 1; and-   m is 1 or 2;-   (12) A compound of formula I, wherein-   R₁ signifies halogen, cyano, nitro, C₁–C₂-alkyl, halo-C₁–C₂-alkyl,    C₁–C₂-alkoxy or halo-C₁–C₂-alkoxy;-   R₃, R₄ and R₅, independently of one another, signify hydrogen,    methyl or halomethyl;-   R₆ signifies hydrogen or C₁–C₂-alkyl;-   R₇ signifies phenyl which is unsubstituted or substituted once or    many times, whereby the substituents may be independent of one    another and are selected from the group consisting of halogen,    cyano, C₁–C₂-alkyl, halo-C₁–C₂-alkyl, C₁–C₂-alkoxy,    halo-C₁–C₂-alkoxy, C₃–C₅-cycloalkyl, C₁–C₂-alkylcarbonyl,    halo-C₁–C₂-alkylcarbonyl, C₁–C₂-alkoxycarbonyl; aryl-C₁–C₂-alkyl    which is unsubstituted or substituted once or many times, and    aryloxy-C₁–C₂-alkyl which is unsubstituted or substituted once or    many times, whereby the substituents may each be independent of one    another and are selected from the group consisting of halogen,    cyano, C₁–C₂-alkyl, halo-C₁–C₂-alkyl, C₁–C₂-alkoxy and    halo-C₁–C₂-alkoxy;-   R₈ and R₉, independently of one another, signify hydrogen or    C₁–C₂-alkyl;-   Y signifies C(O);-   a signifies 1; and-   m is 1 or 2.

Within the context of the invention, particular preference is given tothe compounds of formula I listed in Table 1, and most particularlythose named in the synthesis examples.

A further object of the invention is the process for the preparation ofthe compounds of formula I, respectively in free form or in salt form,for example characterised in that a compound of formula

which is known or may be produced analogously to corresponding knowncompounds, and wherein R₁, R₃, R₄, R₅, R₆, a and m are defined as givenfor formula I, is reacted with a compound of formulaQ—Y—R₇  III,which is known or may be prepared analogously to corresponding knowncompounds, and wherein Y and R₇ are defined as given for formula I and Qis a leaving group, optionally in the presence of a basic catalyst, andif desired, a compound of formula I obtainable according to the methodor in another way, respectively in free form or in salt form, isconverted into another compound of formula I, a mixture of isomersobtainable according to the method is separated and the desired isomerisolated and/or a free compound of formula obtainable according to themethod is converted into a salt or a salt of a compound of formula Iobtainable according to the method is converted into the free compoundof formula I or into another salt.

What has been stated above for salts of compounds I also appliesanalogously to salts of the starting materials listed hereinabove andhereinbelow.

The reaction partners can be reacted with one another as they are, i.e.without the addition of a solvent or diluent, e.g. in the melt. In mostcases, however, the addition of an inert Solvent or diluent, or amixture thereof, is of advantage. Examples of such solvents or diluentsare: aromatic, aliphatic and alicyclic hydrocarbons and halogenatedhydrocarbons, such as benzene, toluene, xylene, mesitylene, tetraline,chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane,cyclohexane, dichloromethane, trichloromethane, tetrachloromethane,dichloroethane, trichloroethene or tetrachloroethene; ethers, such asdiethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether,tert-butyl methyl ether, ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, ethylene glycol dimethylether,dimethoxydiethylether, tetrahydrofuran or dioxane; ketones such asacetone, methyl ethyl ketone or methyl isobutyl ketone; amides such asN,N-dimethylformamide, N,N-diethyl-formamide, N,N-dimethylacetamide,N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles suchas acetonitrile or propionitrile; and sulfoxides, such as dimethylsulfoxide.

Preferred leaving groups are halogens, especially chlorine.

Suitable bases for facilitating the reaction are e.g. alkali metal oralkaline earth metal hydroxides, hydrides, amides, alkanolates,acetates, carbonates, dialkylamides or alkylsilyl-amides; alkylamines,alkylenediamines, optionally N-alkylated, optionally unsaturated,cyclo-alkylamines, basic heterocycles, ammonium hydroxides, as well ascarbocyclic amines. Those which may be mentioned by way of example aresodium hydroxide, hydride, amide, methanolate, acetate, carbonate,potassium tert.-butanolate, hydroxide, carbonate, hydride, lithiumdiisopropylamide, potassium bis(trimethylsilyl)-amide, calcium hydride,triethylamine, diisopropylethylamine, triethylenediamine,cyclohexylamine, N-cyclohexyl-N,N-dimethyl-amine, N,N-diethylaniline,pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine,N-methyl-morpholine, benzyltrimethylammonium hydroxide, as well as1,5-diazabicyclo[5.4.0]undec-5-ene (DBU). Preference is given todiisopropylethylamine and 4-(N,N-dimethylamino)pyridine.

The reaction advantageously takes place in a temperature range of ca. 0°C. to ca. 100° C., preferably from ca. 10° C. to ca. 40° C.

In a preferred process, a compound of formula II is reacted at roomtemperature in a halogenated hydrocarbon, preferably dichloromethane,with a compound of formula III in the presence of a base, preferably amixture of diisopropylethylamine and 4-(N,N-dimethylamino)pyridine.

A further object of the invention is the process for the preparation ofthe compounds of formula II, respectively in free form or in salt form,for example characterised in that a compound of formula

which is known or may be produced analogously to corresponding knowncompounds, in which R₁, R₃, R₄, R₅, a and m are defined as for formulaI, is reacted with an inorganic or organic cyanide and a compound offormula R₆—NH₂, which is known or may be produced analogously tocorresponding known compounds and wherein R₆ is defined as for formulaI, and if desired, a compound of formula II obtainable according to themethod or in another way, respectively in free form or in salt form, isconverted into another compound of formula II, a mixture of isomersobtainable according to the method is separated and the desired isomerisolated and/or a free compound of formula II obtainable according tothe method is converted into a salt or a salt of a compound of formulaII obtainable according to the method is converted into the freecompound of formula II or into another salt.

Suitable cyanides are sodium cyanide, potassium cyanide, trimethylsilylcyanide and acetone cyanohydrin.

The general method for reacting carbonyl compounds, e.g. of formula IV,with cyanides and amines, e.g. of formula R₆—NH₂, is a Streckerreaction, for example as in Organic Synthesis Coll. Vol. 3, 88 (1973).

Salts of compounds I may be produced in known manner. Acid additionsalts of compounds I, for example, are obtainable by treatment with asuitable acid or a suitable ion exchange reagent, and salts with basesare obtainable by treatment with a suitable base or a suitable ionexchange reagent.

Salts of compounds I can be converted into the free compounds I by theusual means, acid addition salts e.g. by treating with a suitable basiccomposition or with a suitable ion exchange reagent, and salts withbases e.g. by treating with a suitable acid or a suitable ion exchangereagent.

Salts of compounds I can be converted into other salts of compounds I ina known manner; acid addition salts can be converted for example intoother acid addition salts, e.g. by treating a salt of an inorganic acid,such as a hydrochloride, with a suitable metal salt, such as a sodium,barium, or silver salt, of an acid, e.g. with silver acetate, in asuitable solvent, in which a resulting inorganic salt, e.g. silverchloride, is insoluble and thus precipitates out from the reactionmixture.

Depending on the method and/or reaction conditions, compounds I withsalt-forming characteristics can be obtained in free form or in the formof salts.

Salts of compounds I may be produced in known manner. Acid additionsalts of compounds I, for example, are obtainable by treatment with asuitable acid or a suitable ion exchange reagent, and salts with basesare obtainable by treatment with a suitable base or a suitable ionexchange reagent.

Salts of compounds I can be converted into the free compounds I by theusual means, acid addition salts e.g. by treating with a suitable basiccomposition or with a suitable ion exchange reagent, and salts withbases e.g. by treating with a suitable acid or a suitable ion exchangereagent.

Salts of compounds I can be converted into other salts of compounds I ina known manner; acid addition salts can be converted for example intoother acid addition salts, e.g. by treating a salt of an inorganic acid,such as a hydrochloride, with a suitable metal salt, such as a sodium,barium, or silver salt, of an acid, e.g. with silver acetate, in asuitable solvent, in which a resulting inorganic salt, e.g. silverchloride, is insoluble and thus precipitates out from the reactionmixture.

Compounds I can also be obtained in the form of their hydrates and/oralso can include other solvents, used for example where necessary forthe crystallisation of compounds present in solid form.

Compounds I and II may be optionally present as optical and/or geometricisomers or as a mixture thereof. The invention relates both to the pureisomers and to all possible isomeric mixtures, and is hereinbefore andhereinafter understood as doing so, even if stereochemical details arenot specifically mentioned in every case.

Diastereoisomeric mixtures of compounds I, which are obtainable by theprocess or in another way, may be separated in known manner, on thebasis of the physical-chemical differences in their components, into thepure diastereoisomers, for example by fractional crystallisation,distillation and/or chromatography.

Splitting of mixtures of enantiomers, that are obtainable accordingly,into the pure isomers, may be achieved by known methods, for example byrecrystallisation from an optically active solvent, by chromatography onchiral adsorbents, e.g. high-pressure liquid chromatography (HPLC) onacetyl cellulose, with the assistance of appropriate micro-organisms, bycleavage with specific immobilised enzymes, through the formation ofinclusion compounds, e.g. using chiral crown ethers, whereby only oneenantiomer is complexed.

According to the invention, apart from separation of correspondingisomer mixtures, generally known methods of diastereoselective orenantioselective synthesis can also be applied to obtain purediastereolsomers or enantiomers, e.g. by carrying out the method of theinvention using educts with correspondingly suitable stereochemistry.

It is advantageous to isolate or synthesise the biologically more activeisomer, e.g. enantiomer, or isomer mixture, e.g. enantiomer mixture,provided that the individual components have differing biologicalefficacy.

In the method of the present invention, the starting materials andintermediates used are preferably those that lead to the compounds Idescribed at the beginning as being especially useful.

The invention relates especially to the method of preparation describedin the example.

Starting materials and intermediates, which are new and are usedaccording to the invention for the preparation of compounds I, as wellas their usage and process for the preparation thereof, similarly forman object of the invention.

The compounds I according to the invention are notable for theirparticularly broad activity spectrum and are valuable active ingredientsfor use in pest control, including in particular the control of endo-and ecto-parasites on animals, whilst being well-tolerated bywarm-blooded animals, fish and plants,

In the context of the present invention, ectoparasites are understood tobe in particular insects, mites and ticks. These include insects of theorder: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera,Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura,Isoptera, Psocoptera and Hymenoptera. However, the ectoparasites whichmay be mentioned in particular are those which trouble humans or animalsand carry pathogens, for example flies such as Musca domestica, Muscavetustissima, Musca autumnalis, Fannia canicularis, Sarcophaga carnaria,Lucilia cuprina, Hypoderma bovis, Hypoderma lineatum, Chrysomyiachloropyga, Dermatobia hominis, Cochliomyia hominivorax, Gasterophilusintestinalis, Oestrus ovis, Stomoxys calcitrans, Haematobia irritans andmidges (Nematocera), such as Culicidae, Simullidae, Psychodidae, butalso blood-sucking parasites, for example fleas, such as Ctenocephalidesfelis and Ctenocephalides canis (cat and dog fleas), Xenopsylla cheopis,Pulex irritans, Dermatophilus penetrans, lice, such as Damalina ovis,Pediculus humanis, biting flies and horse-flies (Tabanidae), Haematopotaspp. such as Haematopota pluvialis, Tabanidea spp. such as Tabanusnigrovittatus, Chrysopsinae spp. such as Chrysops caecutiens, tsetseflies, such as species of Glossinia, biting insects, particularlycockroaches, such as Blatella germanica, Blatta orientalls, Periplanetaamericana, mites, such as Dermanyssus gallinae, Sarcoptes scabiei,Psoroptes ovis and Psorergates spp. and last but not least ticks. Thelatter belong to the order Acarina. Known representatives of ticks are,for example, Boophilus, Amblyomma, Anocentor, Dermacentor,Haemaphysalis, Hyalomma, Ixodes, Rhipicentor, Margaropus, Rhipicephalus,Argas, Otobius and Ornithodoros and the like, which preferably infestwarm-blooded animals including farm animals, such as cattle, pigs, sheepand goats, poultry such as chickens, turkeys and geese, fur-bearinganimals such as mink, foxes, chinchillas, rabbits and the like, as wellas domestic animals such as cats and dogs, but also humans.

Compounds I can also be used against hygiene pests, especially of theorder Diptera of the families Sarcophagidae, Anophilidae and Culicidae;the orders Orthoptera, Dictyoptera (e.g. the family Blattidae) andHymenoptera (e.g. the family Formicidae).

Compounds I also have sustainable efficacy on parasitic mites andinsects of plants. In the case of spider mites of the order Acarina,they are effective against eggs, nymphs and adults of Tetranychidae(Tetranychus spp. and Panonychus spp.).

They have high activity against sucking insects of the order Homoptera,especially against pests of the families Aphididae, Delphacidae,Cicadellidae, Psyllidae, Loccidae, Diaspididae and Eriophydidae (e.g.rust mite on citrus fruits); the orders Hemiptera, Heteroptera andThysanoptera, and on the plant-eating insects of the orders Lepidoptera,Coleoptera, Diptera and Orthoptera

They are similarly suitable as a soil insecticide against pests in thesoil.

The compounds of formula I are therefore effective against all stages ofdevelopment of sucking insects and eating insects on crops such ascereals, cotton, rice, maize, soya, potatoes, vegetables, fruit,tobacco, hops, citrus, avocados and other crops.

The compounds of formula I are also effective against plant nematodes ofthe species Meloidogyne, Heterodera, Pratylenchus, Ditylenchus,Radopholus, Rizoglyphus etc.

In particular, the compounds are effective against helminths, in whichthe endoparasitic nematodes and trematodes may be the cause of seriousdiseases of mammals and poultry, e.g. sheep, pigs, goats, cattle,horses, donkeys, dogs, cats, guinea-pigs and exotic birds. Typicalnematodes of this indication are: Haemonchus, Trichostrongylus,Ostertagia, Nematodirus, Cooperia, Ascaris, Bunostonum, Oesophagostonum,Charbertia, Trichuris, Strongylus, Trichonema, Dictyocaulus, Capillaria,Heterakis, Toxocara, Ascaridia, Oxyuris, Ancylostoma, Uncinaria,Toxascaris and Parascaris. The trematodes include, in particular, thefamily of Fasciolideae, especially Fasciola hepatica. The particularadvantage of the compounds of formula I is their efficacy against thoseparasites that are resistant towards active ingredients based onbenzimidazole.

Certain pests of the species Nematodirus, Cooperia and Oesophagostonuminfest the intestinal tract of the host animal, while others of thespecies Haemonchus and Ostertagia are parasitic in the stomach and thoseof the species Dictyocaulus are parasitic in the lung tissue. Parasitesof the families Filarlidae and Setariidae may be found in the internalcell tissue and in the organs, e.g. the heart, the blood vessels, thelymph vessels and the subcutaneous tissue. A particularly notableparasite is the heartworm of the dog, Dirofilaria immitis. The compoundsof formula I are highly effective against these parasites.

Furthermore, the compounds of formula I are suitable for the control ofhuman pathogenic parasites. Of these, typical representatives thatappear in the digestive tract are those of the species Ancylostoma,Necator, Ascaris, Strongyloides, Trichinella, Capillaria, Trichuris andEnterobius. The compounds of the present invention are also effectiveagainst parasites of the species Wuchereria, Brugia, Onchocerca and Loafrom the family of Filarlidae, which appear in the blood, in the tissueand in various organs, and also against Dracunculus and parasites of thespecies Strongyloides and Trichinella, which infect the gastrointestinaltract in particular.

Finally, the compounds of formula I also have fungicidal andbactericidal activity.

The good pesticidal activity of the compounds of formula I according tothe invention corresponds to a mortality rate of at least 50–60% of thepests mentioned. In particular, the compounds of formula I are notablefor the exceptionally long duration of efficacy.

The compounds of formula I are preferably employed in unmodified form orpreferably together with the adjuvants conventionally used in the art offormulation and may therefore be processed in a known manner to give,for example, emulsifiable concentrates, directly dilutable solutions,dilute emulsions, soluble powders, granules or microencapsulations inpolymeric substances. As with the compositions, the methods ofapplication are selected in accordance with the intended objectives andthe prevailing circumstances.

The formulation, i.e. the agents, preparations or compositionscontaining the active ingredient of formula I, or combinations of theseactive ingredients with other active ingredients, and optionally a solidor liquid adjuvant, are produced in a manner known per se, for exampleby intimately mixing and/or grinding the active ingredients withspreading compositions, for example with solvents, solid carriers, andoptionally surface-active compounds (surfactants).

The solvents in question may be: alcohols, such as ethanol, propanol orbutanol, and glycols and their ethers and esters, such as propyleneglycol, dipropylene glycol ether, ethylene glycol, ethylene glycolmonomethyl or -ethyl ether, ketones, such as cyclohexanone, isophoroneor diacetanol alcohol, strong polar solvents, such asN-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, orwater, vegetable oils, such as rape, castor, coconut, or soybean oil,and also, if appropriate, silicone oils.

Preferred application forms for usage on warm-blooded animals in thecontrol of helminths include solutions, emulsions, suspensions(drenches), food additives, powders, tablets including effervescenttablets, boli, capsules, micro-capsules and pour-on formulations,whereby the physiological compatibility of the formulation excipientsmust be taken into consideration.

The binders for tablets and boli may be chemically modified polymericnatural substances that are soluble in water or in alcohol, such asstarch, cellulose or protein derivatives (e.g. methyl cellulose,carboxymethyl cellulose, ethylhydroxyethyl cellulose, proteins such aszein, gelatin and the like), as well as synthetic polymers, such aspolyvinyl alcohol, polyvinyl pyrrolidone etc. The tablets also containfillers (e.g. starch, microcrystalline cellulose, sugar, lactose etc.),glidants and disintegrants.

If the anthelminthics are present in the form of feed concentrates, thenthe carriers used are e.g. performance feeds, feed grain or proteinconcentrates. Such feed concentrates or compositions may contain, apartfrom the active ingredients, also additives, vitamins, antibiotics,chemotherapeutics or other pesticides, primarily bacteriostats,fungistats, coccidiostats, or even hormone preparations, substanceshaving anabolic action or substances which promote growth, which affectthe quality of meat of animals for slaughter or which are beneficial tothe organism in another way. If the compositions or the activeingredients of formula I contained therein are added directly to feed orto the drinking troughs, then the formulated feed or drink contains theactive ingredients preferably in a concentration of ca. 0.0005 to 0.02%by weight (5–200 ppm).

The compounds of formula I according to the invention may be used aloneor in combination with other biocides. They may be combined withpesticides having the same sphere of activity e.g. to increase activity,or with substances having another sphere of activity e.g. to broaden therange of activity. It can also be sensible to add so-called repellents.If the range of activity is to be extended to endoparasites, e.g.wormers, the compounds of formula I are suitably combined withsubstances having endoparasitic properties. Of course, they can also beused in combination with antibacterial compositions. Since the compoundsof formula I are adulticides, i.e. since they are effective inparticular against the adult stages of the target parasites, theaddition of pesticides which instead attack the juvenile stages of theparasites may be very advantageous. In this way, the greatest part ofthose parasites that produce great economic damage will be covered.Moreover, this action will contribute substantially to avoiding theformation of resistance. Many combinations may also lead to synergisticeffects, i.e. the total amount of active ingredient can be reduced,which is desirable from an ecological point of view. Preferred groups ofcombination partners and especially preferred combination partners arenamed in the following, whereby combinations may contain one or more ofthese partners in addition to a compound of formula I.

Suitable partners in the mixture may be biocides, e.g. the insecticidesand acaricides with a varying mechanism of activity, which are named inthe following and have been known to the person skilled in the art for along time, e.g. chitin synthesis inhibitors, growth regulators; activeingredients which act as juvenile hormones; active ingredients which actas adulticides; broad-band insecticides, broad-band acaricides andnematicides; and also the well known anthelminthics and insect- and/oracarid-deterring substances, said repellents or detachers.

Non-limitative examples of suitable insecticides and acaricides are:

1. Abamectin 2. AC 303 630 3. Acephat 4. Acrinathrin 5. Alanycarb 6.Aldicarb 7. α-Cypermethrin 8. Alphamethrin 9. Amitraz 10. Avermectin B₁11. AZ 60541 12. Azinphos A 13. Azinphos M 14. Azinphos-methyl 15.Azocyclotin 16. Bacillus subtil. toxin 17. Bendiocarb 18. Benfuracarb19. Bensultap 20. β-Cyfluthrin 21. Bifenthrin 22. BPMC 23. Brofenprox24. Bromophos A 25. Bufencarb 26. Buprofezin 27. Butocarboxin 28.Butylpyridaben 29. Cadusafos 30. Carbaryl 31. Carbofuran 32.Carbophenthion 33. Cartap 34. Chloethocarb 35. Chlorethoxyfos 36.Chlorfenapyr 37. Chlorfluazuron 38. Chlormephos 39. Chlorpyrifos 40.Cis-Resmethrin 41. Clocythrin 42. Clofentezin 43. Cyanophos 44.Cycloprothrin 45. Cyfluthrin 46. Cyhexatin 47. D 2341 48. Deltamethrin49. Demeton M 50. Demeton S 51. Demeton-S-methyl 52. Dibutylaminothio53. Dichlofenthion 54. Dicliphos 55. Diethion 56. Diflubenzuron 57.Dimethoat 58. Dimethylvinphos 59. Dioxathion 60. DPX-MP062 61.Edifenphos 62. Emamectin 63. Endosulfan 64. Esfenvalerat 65.Ethiofencarb 66. Ethion 67. Ethofenprox 68. Ethoprophos 69. Etrimphos70. Fenamiphos 71. Fenazaquin 72. Fenbutatinoxid 73. Fenitrothion 74.Fenobucarb 75. Fenothiocarb 76. Fenoxycarb 77. Fenpropathrin 78.Fenpyrad 79. Fenpyroximate 80. Fenthion 81. Fenvalerate 82. Fipronil 83.Fluazinam 84. Fluazuron 85. Flucycloxuron 86. Flucythrinat 87.Flufenoxuron 88. Flufenprox 89. Fonophos 90. Formothion 91. Fosthiazat92. Fubfenprox 93. HCH 94. Heptenophos 95. Hexaflumuron 96. Hexythiazox97. Hydroprene 98. Imidacloprid 99. insect-active fungi 100.insect-active nematodes 101. insect-active viruses 102. Iprobenfos 103.Isofenphos 104. Isoprocarb 105. Isoxathion 106. Ivermectin 107.λ-Cyhalothrin 108. Lufenuron 109. Malathion 110. Mecarbam 111.Mesulfenphos 112. Metaldehyd 113. Methamidophos 114. Methiocarb 115.Methomyl 116. Methoprene 117. Metolcarb 118. Mevinphos 119. Milbemectin120. Moxidectin 121. Naled 122. NC 184 123. NI-25, Acetamiprid 124.Nitenpyram 125. Omethoat 126. Oxamyl 127. Oxydemethon M 128. Oxydeprofos129. Parathion 130. Parathion-methyl 131. Permethrin 132. Phenthoat 133.Phorat 134. Phosalone 135. Phosmet 136. Phoxim 137. Pirimicarb 138.Pirimiphos A 139. Pirimiphos M 140. Promecarb 141. Propaphos 142.Propoxur 143. Prothiofos 144. Prothoat 145. Pyrachlophos 146.Pyradaphenthion 147. Pyresmethrin 148. Pyrethrum 149. Pyridaben 150.Pyrimidifen 151. Pyriproxyfen 152. RH 5992 153. RH-2485 154. Salithion155. Sebufos 156. Silafluofen 157. Spinosad 158. Sulfotep 159. Sulprofos160. Tebufenozide 161. Tebufenpyrad 162. Tebupirimphos 163.Teflubenzuron 164. Tefluthrin 165. Temephos 166. Terbam 167. Terbufos168. Tetrachlorvinphos 169. Thiafenox 170. Thiodicarb 171. Thiofanox172. Thionazin 173. Thuringiensin 174. Tralomethrin 175. Triarthen 176.Triazamate 177. Triazophos 178. Triazuron 179. Trichlorfon 180.Triflumuron 181. Trimethacarb 182. Vamidothion 183. XMC (3,5,-xylyl-methylcarbamate) 184. Xylylcarb 185. YI 5301/5302 186. ζ-Cypermethrin187. ZetamethrinNon-limitative examples of suitable anthelminthics are named in thefollowing, a few representatives have insecticidal and acaricidalactivity in addition to the anthelminthic activity, and are partlyalready in the above list.

-   (A1)    Praziguantel=2-cyclohexylcarbonyl-4-oxo-1,2,3,6,7,11b-hexahydro-4H-pyrazino[2,1-α]isoquinoline-   (A2)    Closantel=3,5-diiodo-N-[5-chloro-2-methyl-4-(a-cyano-4-chlorobenzyl)phenyl]-salicylamide-   (A3)    Triclabendazole=5-chloro-6-(2,3-dichlorophenoxy)-2-methylthio-1H-benzimidazole-   (A4) Levamisol=L-(−)-2,3,5,6-tetrahydro-6-phenylimidazo[2,1    b]thiazole-   (A5) Mebendazole=(5-benzoyl-1H-benzimidazol-2-yl)carbaminic acid    methylester-   (A6) Omphalotin=a macrocyclic fermentation product of the fungus    Omphalotus olearius described in WO 97/20857-   (A7) Abamectin=avermectin B1-   (A8) Ivermectin=22,23-dihydroavermectin B1-   (A9)    Moxidectin=5-O-demethyl-28-deoxy-25-(1,3-dimethyl-1-butenyl)-6,28-epoxy-23-(methoxyimino)-milbemycin    B-   (A10)    Doramectin=25-cyclohexyl-5-O-demethyl-25-de(1-methylpropyl)-avermectin    A1a-   (A11) Milbemectin=mixture of milbemycin A3 and milbemycin A4-   (A12) Milbemycinoxim=5-oxime of milbemectin    Non-limitative examples of suitable repellents and detachers are:-   (R1) DEET (N,N-diethyl-m-toluamide)-   (R2) KBR 3023 N-butyl-2-oxycarbonyl-(2-hydroxy)-piperidine-   (R3)    Cymiazole=N,-2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene-2,4-xylidene

The said partners in the mixture are best known to specialists in thisfield. Most are described in various editions of the Pesticide Manual,The British Crop Protection Council, London, and others in the variouseditions of The Merck Index, Merck & Co., Inc., Rahway, N.J., USA or inpatent literature. Therefore, the following listing is restricted to afew places where they may be found by way of example.

-   (I) 2-Methyl-2-(methylthio)propionaldehyde-O-methylcarbamoyloxime    (Aldicarb), from The Pesticide Manual, 11^(th) Ed. (1997), The    British Crop Protection Council, London, page 26;-   (II)    S-(3,4-dihydro-4-oxobenzo[d]-[1,2,3]-triazin-3-ylmethyl)O,O-dimethyl-phosphoro-dithioate    (Azinphos-methyl), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 67;-   (III)    Ethyl-N-[2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl-(methyl)aminothio]-N-isopropyl-β-alaninate    (Benfuracarb), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 96;-   (IV)    2-Methylbiphenyl-3-ylmethyl-(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate    (Bifenthrin), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 118;-   (V) 2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazian-4-one    (Buprofezin), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 157;-   (VI) 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-methylcarbamate    (Carbofuran), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 186;-   (VII)    2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-(dibutylaminothio)methylcarbamate    (Carbosulfan), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 188;-   (VIII) S,S′-(2-dimethylaminotrimethylene)-bis(thiocarbamate)    (Cartap), from The Pesticide Manual, 11^(th)Ed. (1997), The British    Crop Protection Council, London, page 193;-   (IX)    1-[3,5-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-3-(2,6-difluorobenzoyl)-urea    (Chlorfluazuron), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 213;-   (X) O,O-diethyl-O-3,5,6-trichloro-2-pyridyl-phosphorothioate    (Chlorpyrifos), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 235;-   (XI)    (RS)-α-cyano-4-fluoro-3-phenoxybenzyl-(1RS,3RS;1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-di-methylcyclopropanecarboxylate    (Cyfluthrin), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 293;-   (XII) Mixture of    (S)-α-cyano-3-phenoxybenzyl-(Z)-(1R,3R)-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate    and    (R)-α-cyano-3-phenoxybenzyl-(Z)-(1R,3R)-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate    (Lambda-Cyhalothrin), from The Pesticide Manual, 11^(th)Ed. (1997),    The British Crop Protection Council, London, page 300;-   (XIII) Racemate consisting of    (S)-α-cyano-3-phenoxybenzyl-(Z)-(1R,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate    and    (R)-α-cyano-3-phenoxybenzyl-(1S,3S)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate    (Alpha-cypermethrin), from The Pesticide Manual, 11^(th)Ed. (1997),    The British Crop Protection Council, London, page 308;-   (XIV) a mixture of the stereoisomers of (S)-α-cyano-3-phenoxybenzyl    (1RS,3RS,-1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate    (zeta-Cypermethrin), from The Pesticide Manual, 11^(th)Ed. (1997),    The British Crop Protection Council, London, page 314;-   (XV)    (S)-α-cyano-3-phenoxybenzyl-(1R,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate    (Deltamethrin), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 344;-   (XVI) (4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (Diflubenzuron),    from The Pesticide Manual, 11^(th)Ed. (1997), The British Crop    Protection Council, London, page 395;-   (XVII)    (1,4,5,6,7,7-Hexachloro-8,9,10-trinorborn-5-en-2,3-ylenebismethylene)-sulphite    (Endosulfan), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 459;-   (XVIII) α-ethylthio-o-tolyl-methylcarbamate (Ethiofencarb), from The    Pesticide Manual, 11^(th)Ed. (1997), The British Crop Protection    Council, London, page 479;-   (XIX) O,O-dimethyl-O-4-nitro-m-tolyl-phosphorothioate    (Fenitrothion), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 514;-   (XX) 2-secbutylphenyl-methylcarbamate (Fenobucarb), from The    Pesticide Manual, 11^(th)Ed. (1997), The British Crop Protection    Council, London, page 516;-   (XXI)    (RS)-α-cyano-3-phenoxybenzyl-(RS)-2-(4-chlorophenyl)-3-methylbutyrate    (Fenvalerate), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 539;-   (XXII)    S-[formyl(methyl)carbamoylmethyl]-O,O-dimethyl-phosphorodithioate    (Formothion), from The Pesticide Manual, 11 ^(th)Ed. (1997), The    British Crop Protection Council, London, page 625;-   (XXIII) 4-Methylthio-3,5-xylyl-methylcarbamate (Methiocarb), from    The Pesticide Manual, 11^(th)Ed. (1997), The British Crop Protection    Council, London, page 813;-   (XXIV) 7-Chlorobicyclo[3.2.0]hepta-2,6-dien-6-yl-dimethylphosphate    (Heptenophos), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 670;-   (XXV) 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylidenamine    (Imidacloprid), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 706;-   (XXVI) 2-isopropylphenyl-methylcarbamate (Isoprocarb), from The    Pesticide Manual, 11^(th)Ed. (1997), The British Crop Protection    Council, London, page 729;-   (XXVII) O,S-dimethyl-phosphoramidothioate (Methamidophos), from The    Pesticide Manual, 11^(th)Ed. (1997), The British Crop Protection    Council, London, page 808;-   (XXVIII) S-Methyl-N-(methylcarbamoyloxy)thioacetimidate (Methomyl),    from The Pesticide Manual, 11^(th)Ed. (1997), The British Crop    Protection Council, London, page 815;-   (XXIX) Methyl-3-(dimethoxyphosphinoyloxy)but-2-enoate (Mevinphos),    from The Pesticide Manual, 11^(th)Ed. (1997), The British Crop    Protection Council, London, page 844;-   (XXX) O,O-diethyl-O-4-nitrophenyl-phosphorothioate (Parathion), from    The Pesticide Manual, 11^(th)Ed. (1997), The British Crop Protection    Council, London, page 926;-   (XXXI) O,O-dimethyl-O-4-nitrophenyl-phosphorothioate    (Parathion-methyl), from The Pesticide Manual, 11^(th) Ed. (1997),    The British Crop Protection Council, London, page 928;-   (XXXII)    S-6-chloro-2,3-dihydro-2-oxo-1,3-benzoxazol-3-ylmethyl-O,O-diethyl-phosphor-dithioate    (Phosalone), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 963;-   (XXXIII)    2-Dimethylamino-5,6-dimethylpyrimidin-4-yl-dimethylcarbamate    (Pirimicarb), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 985;-   (XXXIV) 2-isopropoxyphenyl-methylcarbamate (Propoxur), from The    Pesticide Manual, 11^(th)Ed. (1997), The British Crop Protection    Council, London, page 1036;-   (XXXV)    1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea    (Teflubenzuron), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 1158;-   (XXXVI) S-tert-butylthiomethyl-O,O-dimethyl-phosphorodithioate    (Terbufos), from The Pesticide Manual, 11^(th) Ed. (1997), The    British Crop Protection Council, London, page 1165;-   (XXXVII)    ethyl-(3-tert.-butyl-1-dimethylcarbamoyl-1H-1,2,4-triazol-5-yl-thio)-acetate,    (Triazamate), from The Pesticide Manual, 11 ^(th)Ed. (1997), The    British Crop Protection Council, London, page 1224;-   (XXXVIII) Abamectin, from The Pesticide Manual, 11^(th)Ed. (1997),    The British Crop Protection Council, London, page 3;-   (XXXIX) 2-sec-butylphenyl-methylcarbamate (Fenobucarb), from The    Pesticide Manual, 11^(th)Ed. (1997), The British Crop Protection    Council, London, page 516;-   (XL) N-tert.-butyl-N-(4-ethylbenzoyl)-3,5-dimethylbenzohydrazide    (Tebufenozide), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 1147;-   (XLI)    (±)-5-amino-1-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)-4-trifluoromethyl-sulphinylpyrazol-3-carbonitrile    (Fipronil), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 545;-   (XLII)    (RS)-α-cyano-4-fluoro-3-phenoxybenzyl(1RS,3RS;1RS,3RS)-3-(2,2-dichloro-vinyl)-2,2-dimethylcyclopropanecarboxylate    (beta-Cyfluthrin), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 295;-   (XLIII)    (4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl)propyl](dimethyl)silane    (Silafluofen), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 1105;-   (XLIV) tert.-butyl    (E)-α-(1,3-dimethyl-5-phenoxypyrazol-4-yl-methylenamino-oxy)-p-toluate    (Fenpyroximate), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 530;-   (XLV) 2-tert.-butyl-5-(4-tert.-butylbenzylthio)-4-chloropyridazin-3    (2H)-one (Pyridaben), from The Pesticide Manual, 11^(th)Ed. (1997),    The British Crop Protection Council, London, page 1161;-   (XLVI) 4-[[4-(1,1-dimethylphenyl)phenyl]ethoxy]-quinazoline    (Fenazaquin), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 507;-   (XLVII) 4-phenoxyphenyl-(RS)-2-(pyridyloxy)propyl-ether    (Pyriproxyfen), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 1073;-   (XLVIII)    5-chloro-N-[2-[4-(2-ethoxyethyl)-2,3-dimethylphenoxy]ethyl)-6-ethylpyrimidine-4-amine    (Pyrimidifen), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 1070;-   (XLIX)    (E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-N′-methyl-2-nitrovinylidenediamine    (Nitenpyram), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 880;-   (L) (E)-N¹-(6-chloro-3-pyridyl)methyl]-N²-cyano-N¹-methylacetamidine    (NI-25, Acetamiprid), from The Pesticide Manual, 11^(th)ed. (1997),    The British Crop Protection Council, London, page 9;-   (LI) Avermectin B₁, from The Pesticide Manual, 11^(th)Ed. (1997),    The British Crop Protection Council, London, page 3;-   (LII) an insect-active extract from a plant, especially    (2R,6aS,12aS)-1,2,6,6a,12,12a-hexhydro-2-isopropenyl-8,9-dimethoxy-chromeno[3,4-b]furo[2,3-h]chromen-6-one    (Rotenone), from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 1097; and an extract    from Azadirachta indica, especially azadirachtin, from The Pesticide    Manual, 11^(th)Ed. (1997), The British Crop Protection Council,    London, page 59; and-   (LII) a preparation which contains insect-active nematodes,    preferably Heterorhabditis bacteriophora and Heterorhabditis    megidis, from The Pesticide Manual, 11^(th)Ed. (1997), The British    Crop Protection Council, London, page 671; Steinernema feltiae, from    The Pesticide Manual, 11^(th)Ed. (1997), The British Crop Protection    Council, London, page 1115 and Steinernema scapterisci, from The    Pesticide Manual, 11^(th)Ed. (1997), The British Crop Protection    Council, London, page 1116;-   (LIV) a preparation obtainable from Bacillus subtilis, from The    Pesticide Manual, 11^(th)Ed. (1997), The British Crop Protection    Council, London, page 72; or from a strain of Bacillus thuringiensis    with the exception of compounds isolated from GC91 or from    NCTC11821; The Pesticide Manual, 11^(th)Ed. (1997), The British Crop    Protection Council, London, page 73;-   (LV) a preparation which contains insect-active fungi, preferably    Verticillium lecanii, from The Pesticide Manual, 11^(th)Ed. (1997),    The British Crop Protection Council, London, page 1266; Beauveria    brogniartii, from The Pesticide Manual, 11^(th)Ed. (1997), The    British Crop Protection Council, London, page 85 and Beauveria    bassiana, from The Pesticide Manual, 11^(th)Ed. (1997), The British    Crop Protection Council, London, page 83;-   (LVI) a preparation which contains insect-active viruses, preferably    Neodipridon Sertifer NPV, from The Pesticide Manual, 11^(th)Ed.    (1997), The British Crop Protection Council, London, page 1342;    Mamestra brassicae NPV, from The Pesticide Manual, 11^(th) Ed.    (1997), The British Crop Protection Council, London, page 759 and    Cydia pomonella granulosis virus, from The Pesticide Manual,    11^(th)Ed. (1997), The British Crop Protection Council, London, page    291;-   (CLXXXI)    7-chloro-2,3,4a,5-tetrahydro-2-[methoxycarbonyl(4-trifluoromethoxyphenyl)-carbamoyl]indol[1,2e]oxazoline-4a-carboxylate    (DPX-MP062, Indoxycarb), from The Pesticide Manual, 11^(th)Ed.    (1997), The British Crop Protection Council, London, page 453;-   (CLXXXII)    N′-tert.-butyl-N′-(3,5-dimethylbenzoyl)-3-methoxy-2-methylbenzohydrazide    (RH-2485, Methoxyfenozide), from The Pesticide Manual, 11^(th)Ed.    (1997), The British Crop Protection Council, London, page 1094; and-   (CLXXXIII) (N′L[4-methoxy-biphenyl-3-yl]-hydrazinecarboxylic acid    isopropylester (D 2341), from Brighton Crop Protection Conference,    1996, 487–493;-   (R2) Book of Abstracts, 212th ACS National Meeting Orlando, Fla.,    August 25–29 (1996), AGRO-020. Publisher: American Chemical Society,    Washington, D.C. CONEN: 63BFAF.

As a consequence of the above details, a further essential aspect of thepresent invention relates to combination preparations for the control ofparasites on warm-blooded animals, characterised in that they contain,in addition to a compound of formula I, at least one further activeingredient having the same or different sphere of activity and at leastone physiologically acceptable carrier. The present invention is notrestricted to two-fold combinations.

As a rule, the anthelminthic compositions according to the inventioncontain 0.1 to 99% by weight, especially 0.1 to 95% by weight of activeingredient of formula I, Ia or mixtures thereof, 99.9 to 1% by weight,especially 99.8 to 5% by weight of a solid or liquid admixture,including 0 to 25% by weight, especially 0.1 to 25% by weight of asurfactant.

Application of the compositions according to the invention to theanimals to be treated may take place topically, perorally, parenterallyor subcutaneously, the composition being present in the form ofsolutions, emulsions, suspensions, (drenches), powders, tablets, boli,capsules and pour-on formulations.

The pour-on or spot-on method consists in applying the compound offormula I to a specific location of the skin or coat, advantageously tothe neck or backbone of the animal. This takes place e.g. by applying aswab or spray of the pour-on or spot-on formulation to a relativelysmall area of the coat, from where the active substance is dispersedalmost automatically over wide areas of the fur owing to the spreadingnature of the components in the formulation and assisted by the animal'smovements.

Pour-on or spot-on formulations suitably contain carriers, which promoterapid dispersement over the skin surface or in the coat of the hostanimal, and are generally regarded as spreading oils. Suitable carriersare e.g. oily solutions; alcoholic and isopropanolic solutions such assolutions of 2-octyldodecanol or oleyl alcohol; solutions in esters ofmonocarboxylic acids, such as isopropyl myristate, isopropyl palmitate,lauric acid oxalate, oleic acid oleyl ester, oleic acid decyl ester,hexyl laurate, oleyl oleate, decyl oleate, capric acid esters ofsaturated fat alcohols of chain length C₁₂–C₁₈; solutions of esters ofdicarboxylic acids, such as dibutyl phthalate, diisopropyl isophthalate,adipic acid diisopropyl ester, di-n-butyl adipate or also solutions ofesters of aliphatic acids, e.g. glycols. It may be advantageous for adispersing agent to be additionally present, such as one known from thepharmaceutical or cosmetic industry. Examples are 2-pyrrolidone,2-(N-alkyl)pyrrolidone, acetone, polyethylene glycol and the ethers andesters thereof, propylene glycol or synthetic triglycerides.

The oily solutions include e.g. vegetable oils such as olive oil,groundnut oil, sesame oil, pine oil, linseed oil or castor oil. Thevegetable oils may also be present in epoxidised form. Paraffins andsilicone oils may also be used.

A pour-on or spot-on formulation generally contains 1 to 20% by weightof a compound of formula I, 0.1 to 50% by weight of dispersing agent and45 to 98.9% by weight of solvent.

The pour-on or spot-on method is especially advantageous for use on herdanimals such as cattle, horses, sheep or pigs, in which it is difficultor time-consuming to treat all the animals orally or by injection.Because of its simplicity, this method can of course also be used forall other animals, including individual domestic animals or pets, and isgreatly favoured by the keepers of the animals, as it can often becarried out without the specialist presence of the veterinarian.

Whereas it is preferred to formulate commercial products asconcentrates, the end user will normally use dilute formulations.

Such compositions may also contain further additives, such asstabilisers, anti-foaming agents, viscosity regulators, binding agentsor tackifiers, as well as other active ingredients, in order to achievespecial effects.

Anthelminthic compositions of this type, which are used by the end user,similarly form a constituent of the present invention.

In each of the processes according to the invention for pest control orin each of the pest control compositions according to the invention, theactive ingredients of formula I can be used in all of their stericconfigurations or in mixtures thereof.

The invention also includes a method of prophylactically protectingwarm-blooded animals, especially productive livestock, domestic animalsand pets, against parasitic helminths, which is characterised in thatthe active ingredients of the formula or the active ingredientformulations prepared therefrom are administered to the animals as anadditive to the feed, or to the drinks or also in solid or liquid form,orally or by injection or parenterally. The invention also includes thecompounds of formula I according to the invention for usage in one ofthe said processes.

The following examples serve merely to illustrate the invention withoutrestricting it, the term active ingredient representing a substancelisted in tables . . .

In particular, preferred formulations are made up as follows:

(%=percent by weight)

FORMULATION EXAMPLES

1. Granulate a) b) active ingredient 5% 10% kaolin 94%  — highlydispersed silicic acid 1% — attapulgite — 90%

The active ingredient is dissolved in methylene chloride, sprayed ontothe carrier and the solvent subsequently concentrated by evaporationunder vacuum. Granulates of this kind can be mixed with the animal feed.

2. Granulate active ingredient 3% polyethylene glycol (mw 200) 3% kaolin94%  (mw = molecular weight)

The finely ground active ingredient is evenly applied in a mixer to thekaolin which has been moistened with polyethylene glycol. In this way,dust-free coated granules are obtained.

3. Tablets or boli I active ingredient 33.00% methylcellulose 0.80%silicic acid, highly dispersed 0.80% corn starch 8.40% II lactose,cryst. 22.50% corn starch 17.00% microcryst. cellulose 16.50% magnesiumStearate 1.00% I Methyl cellulose is stirred into water. After thematerial has swollen, silicic acid is stirred in and the mixturehomogeneously suspended. The active ingredient and the corn starch aremixed. The aqueous suspension is worked into this mixture and kneaded toa dough. The resulting mass is granulated through a 12 M sieve anddried. II All 4 excipients are mixed thoroughly. III The preliminarymixes obtained according to I and II are mixed and pressed into tabletsor boli.4. InjectablesA. Oily Vehicle (Slow Release)

1. active ingredient 0.1–1.0 g groundnut oil ad 100 ml 2. activeingredient 0.1–1.0 g sesame oil ad 100 ml

Preparation: The active ingredient is dissolved in part of the oilwhilst stirring and, if required, with gentle heating, then aftercooling made up to the desired volume and sterile-filtered through asuitable membrane filter with a pore size of 0.22 mm.

B Water-Miscible Solvent (Average Rate of Release)

active ingredient 0.1–1.0 g 4-hydroxymethyl-1,3-dioxolane 40 g (glycerolformal) 1,2-propanediol ad 100 ml active ingredient 0.1–1.0 g glyceroldimethyl ketal 40 g 1,2-propanediol ad 100 ml

Preparation: The active ingredient is dissolved in part of the solventwhilst stirring, made up to the desired volume and sterile-filteredthrough a suitable membrane filter with a pore size of 0.22 mm.

C. Aqueous Solubilisate (Rapid Release)

1. active ingredient 0.1–1.0 g polyethoxylated castor oil 10 g (40ethylene oxide units) 1,2-propanediol 20 g benzyl alcohol 1 g aqua adinject. ad 100 ml 2. active ingredient 0.1–1.0 g polyethoxylatedsorbitan 8 g monooleate (20 ethylene oxide units)4-hydroxymethyl-1,3-dioxolane 20 g (glycerol formal) benzyl alcohol 1 gaqua ad inject. ad 100 ml

Preparation: The active ingredient is dissolved in the solvents and thesurfactant, and made up with water to the desired volume. Sterilefiltration through an appropriate membrane filter of 0.22 mm pore size.

5. Pour On

A. active ingredient 5 g isopropyl myristate 10 g isopropanol ad 100 mlB active ingredient 2 g hexyl laurate 5 g medium-chained triglyceride 15g ethanol ad 100 ml C. active ingredient 2 g oleyl oleate 5 gN-methyl-pyrrolidone 40 g isopropanol ad 100 ml

The aqueous systems may also preferably be used for oral and/orintraruminal application.

The compositions may also contain further additives, such asstabilisers, e.g. where appropriate epoxidised vegetable oils(epoxidised coconut oil, rapeseed oil, or soybean oil); antifoams, e.g.silicone oil, preservatives, viscosity regulators, binders, tackifiers,as well as fertilisers or other active ingredients to achieve specialeffects.

Further biologically active substances or additives, which are neutraltowards the compounds of formula I and do not have a harmful effect onthe host animal to be treated, as well as mineral salts or vitamins, mayalso be added to the described compositions.

The following examples serve to illustrate the invention. They do notlimit the invention. The letter ‘h’ stands for hour.

PREPARATION EXAMPLES Example 1N-[1-cyano-1-methyl-2-(5-chlorobenzotriazol-1-yl)-ethyl]-4-trifluoromethoxy-benzamide

a) A mixture of 5 g of 5-chlorobenzotriazole, 1.4 g of chloroacetone,5.1 g of potassium carbonate and 0.5 g of potassium iodide is stirredinto 50 ml of acetone at room temperature for 48 h. The mixture issubsequently filtered, the filtrate concentrated by evaporation in avacuum, and the residue purified by flash chromatography. In this way,two isomeric products, 1-(5-chlorobenzotriazol-1-yl)-propan-2-one and1-(6-chlorobenzotriazol-1-yl)-propan-2-one, are isolated inapproximately the same quantities, the first of which is then useddirectly in the next step.

b) 240 mg of 1-(5-chlorobenzotriazol-1-yl)-propan-2-one are dissolved in4 ml of a 2-molar solution of ammonia in ethanol, then 64 mg of sodiumcyanide and 91 mg of ammonium chloride are added and the mixture isstirred over night at room temperature. The reaction mixture issubsequently concentrated by evaporation in a vacuum, dissolved again inethyl acetate, and washed with water and saturated sodium chloridesolution. The organic phase is separated, dried with magnesium sulphateand concentrated by evaporation.2-amino-3-(5-chlorobenzotriazol-1-yl)-2-methylpropionitrile is thusobtained.

c) 258 mg of 2-amino-3-(5-chlorobenzotriazol-1-yl)-2-methylpropionitrileare dissolved in 8 ml of dry dichloromethane, mixed with 194 mg of ethyldiisopropylamine, 16 mg of 4-dimethyl-aminopyridine and 292 mg of4-(2-trifluoromethoxy)-benzoyl chloride and subsequently stirred for 7 hat room temperature. Subsequently, the reaction mixture is diluted withethyl acetate, then washed with a saturated sodium bicarbonate solutionand with saturated sodium chloride solution. After drying the organicphase with magnesium sulphate and concentrating by evaporation, theresidue is recrystallised in diethylether. In this way, the titlecompound is obtained with a melting point of 135° C.

The substances named in the following table may also be preparedanalogously to the above-described method. The values of the meltingpoints are indicated in ° C. Bd. signifies a direct bond.

TABLE 1

No. Y₁ (R₁)_(m) R₇₁ phys. data 1.1 Bd. H H 1.2 Bd. H 2-Cl 1.3 Bd. H 3-Cl1.4 Bd. H 4-Cl 1.5 Bd. H 2-F 1.6 Bd. H 3-F 1.7 Bd. H 4-F 1.8 Bd. H 2-CH₃1.9 Bd. H 3-CH₃ 1.10 Bd. H 4-CH₃ 1.11 Bd. H 2-OCH₃ 1.12 Bd. H 3-OCH₃1.13 Bd. H 4-OCH₃ 1.14 Bd. H 2-CF₃ 1.15 Bd. H 3-CF₃ 1.16 Bd. H 4-CF₃1.17 Bd. H 2-OCF₃ 1.18 Bd. H 3-OCF₃ 1.19 Bd. H 4-OCF₃ 1.20 Bd. H2-OCF₂CF₂ 1.21 Bd. H 3-OCF₂CF₂ 1.22 Bd. H 4-OCF₂CF₂ 1.23 Bd. H 2-OC₂F₅1.24 Bd. H 3-OC₂F₅ 1.25 Bd. H 4-OC₂F₅ 1.26 Bd. H 2-OC₆H₅ 1.27 Bd. H3-OC₆H₅ 1.28 Bd. H 4-OC₆H₅ 1.29 Bd. H 2-C(O)C₆H₅ 1.30 Bd. H 3-C(O)C₆H₅1.31 Bd. H 4-C(O)C₆H₅ 1.32 Bd. H 4-CN 1.33 Bd. 5-Cl H 1.34 Bd. 5-Cl 2-Cl1.35 Bd. 5-Cl 3-Cl 1.36 Bd. 5-Cl 4-Cl 1.37 Bd. 5-Cl 2-F 1.38 Bd. 5-Cl3-F 1.39 Bd. 5-Cl 4-F 1.40 Bd. 5-Cl 2-CH₃ 1.41 Bd. 5-Cl 3-CH₃ 1.42 Bd.5-Cl 4-CH₃ 1.43 Bd. 5-Cl 2-OCH₃ 1.44 Bd. 5-Cl 3-OCH₃ 1.45 Bd. 5-Cl4-OCH₃ 1.46 Bd. 5-Cl 2-CF₃ 1.47 Bd. 5-Cl 3-CF₃ 1.48 Bd. 5-Cl 4-CF₃ 1.49Bd. 5-Cl 2-OCF₃ 1.50 Bd. 5-Cl 3-OCF₃ 1.51 Bd. 5-Cl 4-OCF₃ m.p. 135° 1.52Bd. 5-Cl 2-OCF₂CF₂ 1.53 Bd. 5-Cl 3-OCF₂CF₂ 1.54 Bd. 5-Cl 4-OCF₂CF₂ 1.55Bd. 5-Cl 2-OC₂F₅ 1.56 Bd. 5-Cl 3-OC₂F₅ 1.57 Bd. 5-Cl 4-OC₂F₅ 1.58 Bd.5-Cl 2-OC₆H₅ 1.59 Bd. 5-Cl 3-OC₆H₅ 1.60 Bd. 5-Cl 4-OC₆H₅ 1.61 Bd. 5-Cl2-C(O)C₆H₅ 1.62 Bd. 5-Cl 3-C(O)C₆H₅ 1.63 Bd. 5-Cl 4-C(O)C₆H₅ 1.64 Bd.5-Cl 4-CN 1.65 Bd. 6-Cl H 1.66 Bd. 6-Cl 2-Cl 1.67 Bd. 6-Cl 3-Cl 1.68 Bd.6-Cl 4-Cl 1.69 Bd. 6-Cl 2-F 1.70 Bd. 6-Cl 3-F 1.71 Bd. 6-Cl 4-F 1.72 Bd.6-Cl 2-CH₃ 1.73 Bd. 6-Cl 3-CH₃ 1.74 Bd. 6-Cl 4-CH₃ 1.75 Bd. 6-Cl 2-OCH₃1.76 Bd. 6-Cl 3-OCH₃ 1.77 Bd. 6-Cl 4-OCH₃ 1.78 Bd. 6-Cl 2-CF₃ 1.79 Bd.6-Cl 3-CF₃ 1.80 Bd. 6-Cl 4-CF₃ 1.81 Bd. 6-Cl 2-OCF₃ 1.82 Bd. 6-Cl 3-OCF₃1.83 Bd. 6-Cl 4-OCF₃ m.p. 124° 1.84 Bd. 6-Cl 2-OCF₂CF₂ 1.85 Bd. 6-Cl3-OCF₂CF₂ 1.86 Bd. 6-Cl 4-OCF₂CF₂ 1.87 Bd. 6-Cl 2-OC₂F₅ 1.88 Bd. 6-Cl3-OC₂F₅ 1.89 Bd. 6-Cl 4-OC₂F₅ 1.90 Bd. 6-Cl 2-OC₆H₅ 1.91 Bd. 6-Cl3-OC₆H₅ 1.92 Bd. 6-Cl 4-OC₆H₅ 1.93 Bd. 6-Cl 2-C(O)C₆H₅ 1.94 Bd. 6-Cl3-C(O)C₆H₅ 1.95 Bd. 6-Cl 4-C(O)C₆H₅ 1.96 Bd. 6-Cl 4-CN 1.97 Bd. 5-Cl,6-F H 1.98 Bd. 5-Cl, 6-F 2-Cl 1.99 Bd. 5-Cl, 6-F 3-Cl 1.100 Bd. 5-Cl,6-F 4-Cl 1.101 Bd. 5-Cl, 6-F 2-F 1.102 Bd. 5-Cl, 6-F 3-F 1.103 Bd. 5-Cl,6-F 4-F 1.104 Bd. 5-Cl, 6-F 2-CH₃ 1.105 Bd. 5-Cl, 6-F 3-CH₃ 1.106 Bd.5-Cl, 6-F 4-CH₃ 1.107 Bd. 5-Cl, 6-F 2-OCH₃ 1.108 Bd. 5-Cl, 6-F 3-OCH₃1.109 Bd. 5-Cl, 6-F 4-OCH₃ 1.110 Bd. 5-Cl, 6-F 2-CF₃ 1.111 Bd. 5-Cl, 6-F3-CF₃ 1.112 Bd. 5-Cl, 6-F 4-CF₃ 1.113 Bd. 5-Cl, 6-F 2-OCF₃ 1.114 Bd.5-Cl, 6-F 3-OCF₃ 1.115 Bd. 5-Cl, 6-F 4-OCF₃ solid 1.116 Bd. 5-Cl, 6-F2-OCF₂CF₂ 1.117 Bd. 5-Cl, 6-F 3-OCF₂CF₂ 1.118 Bd. 5-Cl, 6-F 4-OCF₂CF₂1.119 Bd. 5-Cl, 6-F 2-OC₂F₅ 1.120 Bd. 5-Cl, 6-F 3-OC₂F₅ 1.121 Bd. 5-Cl,6-F 4-OC₂F₅ 1.122 Bd. 5-Cl, 6-F 2-OC₆H₅ 1.123 Bd. 5-Cl, 6-F 3-OC₆H₅1.124 Bd. 5-Cl, 6-F 4-OC₆H₅ 1.125 Bd. 5-Cl, 6-F 2-C(O)C₆H₅ 1.126 Bd.5-Cl, 6-F 3-C(O)C₆H₅ 1.127 Bd. 5-Cl, 6-F 4-C(O)C₆H₅ 1.128 Bd. 5-Cl, 6-F4-CN 1.129 Bd. 6-Cl, 5-F H 1.130 Bd. 6-Cl, 5-F 2-Cl 1.131 Bd. 6-Cl, 5-F3-Cl 1.132 Bd. 6-Cl, 5-F 4-Cl 1.133 Bd. 6-Cl, 5-F 2-F 1.134 Bd. 6-Cl,5-F 3-F 1.135 Bd. 6-Cl, 5-F 4-F 1.136 Bd. 6-Cl, 5-F 2-CH₃ 1.137 Bd.6-Cl, 5-F 3-CH₃ 1.138 Bd. 6-Cl, 5-F 4-CH₃ 1.139 Bd. 6-Cl, 5-F 2-OCH₃1.140 Bd. 6-Cl, 5-F 3-OCH₃ 1.141 Bd. 6-Cl, 5-F 4-OCH₃ 1.142 Bd. 6-Cl,5-F 2-CF₃ 1.143 Bd. 6-Cl, 5-F 3-CF₃ 1.144 Bd. 6-Cl, 5-F 4-CF₃ 1.145 Bd.6-Cl, 5-F 2-OCF₃ 1.146 Bd. 6-Cl, 5-F 3-OCF₃ 1.147 Bd. 6-Cl, 5-F 4-OCF₃solid 1.148 Bd. 6-Cl, 5-F 2-OCF₂CF₂ 1.149 Bd. 6-Cl, 5-F 3-OCF₂CF₂ 1.150Bd. 6-Cl, 5-F 4-OCF₂CF₂ 1.151 Bd. 6-Cl, 5-F 2-OC₂F₅ 1.152 Bd. 6-Cl, 5-F3-OC₂F₅ 1.153 Bd. 6-Cl, 5-F 4-OC₂F₅ 1.154 Bd. 6-Cl, 5-F 2-OC₆H₅ 1.155Bd. 6-Cl, 5-F 3-OC₆H₅ 1.156 Bd. 6-Cl, 5-F 4-OC₆H₅ 1.157 Bd. 6-Cl, 5-F2-C(O)C₆H₅ 1.158 Bd. 6-Cl, 5-F 3-C(O)C₆H₅ 1.159 Bd. 6-Cl, 5-F 4-C(O)C₆H₅1.160 Bd. 6-Cl, 5-F 4-CN 1.161 CH₂O H H 1.162 CH₂O H 2-Cl 1.163 CH₂O H3-Cl 1.164 CH₂O H 4-Cl 1.165 CH₂O H 2-F 1.166 CH₂O H 3-F 1.167 CH₂O H4-F 1.168 CH₂O H 2-CH₃ 1.169 CH₂O H 3-CH₃ 1.170 CH₂O H 4-CH₃ 1.171 CH₂OH 2-OCH₃ 1.172 CH₂O H 3-OCH₃ 1.173 CH₂O H 4-OCH₃ 1.174 CH₂O H 2-CF₃1.175 CH₂O H 3-CF₃ 1.176 CH₂O H 4-CF₃ 1.177 CH₂O H 2-OCF₃ 1.178 CH₂O H3-OCF₃ 1.179 CH₂O H 4-OCF₃ 1.180 CH₂O H 2-OCF₂CF₂ 1.181 CH₂O H 3-OCF₂CF₂1.182 CH₂O H 4-OCF₂CF₂ 1.183 CH₂O H 2-OC₂F₅ 1.184 CH₂O H 3-OC₂F₅ 1.185CH₂O H 4-OC₂F₅ 1.186 CH₂O H 2-OC₆H₅ 1.187 CH₂O H 3-OC₆H₅ 1.188 CH₂O H4-OC₆H₅ 1.189 CH₂O H 2-C(O)C₆H₅ 1.190 CH₂O H 3-O(O)C₆H₅ 1.191 CH₂O H4-C(O)C₆H₅ 1.192 CH₂O H 4-CN 1.193 CH₂O 5-Cl H 1.194 CH₂O 5-Cl 2-Cl1.195 CH₂O 5-Cl 3-Cl 1.196 CH₂O 5-Cl 4-Cl 1.197 CH₂O 5-Cl 2-F 1.198 CH₂O5-Cl 3-F 1.199 CH₂O 5-Cl 4-F 1.200 CH₂O 5-Cl 2-CH₃ 1.201 CH₂O 5-Cl 3-CH₃1.202 CH₂O 5-Cl 4-CH₃ 1.203 CH₂O 5-Cl 2-OCH₃ 1.204 CH₂O 5-Cl 3-OCH₃1.205 CH₂O 5-Cl 4-OCH₃ 1.206 CH₂O 5-Cl 2-CF₃ 1.207 CH₂O 5-Cl 3-CF₃ 1.208CH₂O 5-Cl 4-CF₃ 1.209 CH₂O 5-Cl 2-OCF₃ 1.210 CH₂O 5-Cl 3-OCF₃ 1.211 CH₂O5-Cl 4-OCF₃ 1.212 CH₂O 5-Cl 2-OCF₂CF₂ 1.213 CH₂O 5-Cl 3-OCF₂CF₂ 1.214CH₂O 5-Cl 4-OCF₂CF₂ 1.215 CH₂O 5-Cl 2-OC₂F₅ 1.216 CH₂O 5-Cl 3-OC₂F₅1.217 CH₂O 5-Cl 4-OC₂F₅ 1.218 CH₂O 5-Cl 2-OC₆H₅ 1.219 CH₂O 5-Cl 3-OC₆H₅1.220 CH₂O 5-Cl 4-OC₆H₅ 1.221 CH₂O 5-Cl 2-C(O)C₆H₅ 1.222 CH₂O 5-Cl3-C(O)C₆H₅ 1.223 CH₂O 5-Cl 4-C(O)C₆H₅ 1.224 CH₂O 5-Cl 4-CN 1.225 CH₂O6-Cl H 1.226 CH₂O 6-Cl 2-Cl 1.227 CH₂O 6-Cl 3-Cl 1.228 CH₂O 6-Cl 4-Cl1.229 CH₂O 6-Cl 2-F 1.230 CH₂O 6-Cl 3-F 1.231 CH₂O 6-Cl 4-F 1.232 CH₂O6-Cl 2-CH₃ 1.233 CH₂O 6-Cl 3-CH₃ 1.234 CH₂O 6-Cl 4-CH₃ 1.235 CH₂O 6-Cl2-OCH₃ 1.236 CH₂O 6-Cl 3-OCH₃ 1.237 CH₂O 6-Cl 4-OCH₃ 1.238 CH₂O 6-Cl2-CF₃ 1.239 CH₂O 6-Cl 3-CF₃ 1.240 CH₂O 6-Cl 4-CF₃ 1.241 CH₂O 6-Cl 2-OCF₃1.242 CH₂O 6-Cl 3-OCF₃ 1.243 CH₂O 6-Cl 4-OCF₃ 1.244 CH₂O 6-Cl 2-OCF₂CF₂1.245 CH₂O 6-Cl 3-OCF₂CF₂ 1.246 CH₂O 6-Cl 4-OCF₂CF₂ 1.247 CH₂O 6-Cl2-OC₂F₅ 1.248 CH₂O 6-Cl 3-OC₂F₅ 1.249 CH₂O 6-Cl 4-OC₂F₅ 1.250 CH₂O 6-Cl2-OC₆H₅ 1.251 CH₂O 6-Cl 3-OC₆H₅ 1.252 CH₂O 6-Cl 4-OC₆H₅ 1.253 CH₂O 6-Cl2-C(O)C₆H₅ 1.254 CH₂O 6-Cl 3-C(O)C₆H₅ 1.255 CH₂O 6-Cl 4-C(O)C₆H₅ 1.256CH₂O 6-Cl 4-CN 1.257 CH₂O 5-Cl, 6-F H 1.258 CH₂O 5-Cl, 6-F 2-Cl 1.259CH₂O 5-Cl, 6-F 3-Cl 1.260 CH₂O 5-Cl, 6-F 4-Cl 1.261 CH₂O 5-Cl, 6-F 2-F1.262 CH₂O 5-Cl, 6-F 3-F 1.263 CH₂O 5-Cl, 6-F 4-F 1.264 CH₂O 5-Cl, 6-F2-CH₃ 1.265 CH₂O 5-Cl, 6-F 3-CH₃ 1.266 CH₂O 5-Cl, 6-F 4-CH₃ 1.267 CH₂O5-Cl, 6-F 2-OCH₃ 1.268 CH₂O 5-Cl, 6-F 3-OCH₃ 1.269 CH₂O 5-Cl, 6-F 4-OCH₃1.270 CH₂O 5-Cl, 6-F 2-CF₃ 1.271 CH₂O 5-Cl, 6-F 3-CF₃ 1.272 CH₂O 5-Cl,6-F 4-CF₃ 1.273 CH₂O 5-Cl, 6-F 2-OCF₃ 1.274 CH₂O 5-Cl, 6-F 3-OCF₃ 1.275CH₂O 5-Cl, 6-F 4-OCF₃ 1.276 CH₂O 5-Cl, 6-F 2-OCF₂CF₂ 1.277 CH₂O 5-Cl,6-F 3-OCF₂CF₂ 1.278 CH₂O 5-Cl, 6-F 4-OCF₂CF₂ 1.279 CH₂O 5-Cl, 6-F2-OC₂F₅ 1.280 CH₂O 5-Cl, 6-F 3-OC₂F₅ 1.281 CH₂O 5-Cl, 6-F 4-OC₂F₅ 1.282CH₂O 5-Cl, 6-F 2-OC₆H₅ 1.283 CH₂O 5-Cl, 6-F 3-OC₆H₅ 1.284 CH₂O 5-Cl, 6-F4-OC₆H₅ 1.285 CH₂O 5-Cl, 6-F 2-C(O)C₆H₅ 1.286 CH₂O 5-Cl, 6-F 3-C(O)C₆H₅1.287 CH₂O 5-Cl, 6-F 4-C(O)C₆H₅ 1.288 CH₂O 5-Cl, 6-F 4-CN 1.289 CH₂O6-Cl, 5-F H 1.290 CH₂O 6-Cl, 5-F 2-Cl 1.291 CH₂O 6-Cl, 5-F 3-Cl 1.292CH₂O 6-Cl, 5-F 4-Cl 1.293 CH₂O 6-Cl, 5-F 2-F 1.294 CH₂O 6-Cl, 5-F 3-F1.295 CH₂O 6-Cl, 5-F 4-F 1.296 CH₂O 6-Cl, 5-F 2-CH₃ 1.297 CH₂O 6-Cl, 5-F3-CH₃ 1.298 CH₂O 6-Cl, 5-F 4-CH₃ 1.299 CH₂O 6-Cl, 5-F 2-OCH₃ 1.300 CH₂O6-Cl, 5-F 3-OCH₃ 1.301 CH₂O 6-Cl, 5-F 4-OCH₃ 1.302 CH₂O 6-Cl, 5-F 2-CF₃1.303 CH₂O 6-Cl, 5-F 3-CF₃ 1.304 CH₂O 6-Cl, 5-F 4-CF₃ 1.305 CH₂O 6-Cl,5-F 2-OCF₃ 1.306 CH₂O 6-Cl, 5-F 3-OCF₃ 1.307 CH₂O 6-Cl, 5-F 4-OCF₃ 1.308CH₂O 6-Cl, 5-F 2-OCF₂CF₂ 1.309 CH₂O 6-Cl, 5-F 3-OCF₂CF₂ 1.310 CH₂O 6-Cl,5-F 4-OCF₂CF₂ 1.311 CH₂O 6-Cl, 5-F 2-OC₂F₅ 1.312 CH₂O 6-Cl, 5-F 3-OC₂F₅1.313 CH₂O 6-Cl, 5-F 4-OC₂F₅ 1.314 CH₂O 6-Cl, 5-F 2-OC₆H₅ 1.315 CH₂O6-Cl, 5-F 3-OC₆H₅ 1.316 CH₂O 6-Cl, 5-F 4-OC₆H₅ 1.317 CH₂O 6-Cl, 5-F2-C(O)C₆H₅ 1.318 CH₂O 6-Cl, 5-F 3-C(O)C₆H₅ 1.319 CH₂O 6-Cl, 5-F4-C(O)C₆H₅ 1.320 CH₂O 6-Cl, 5-F 4-CN

BIOLOGICAL EXAMPLES

1. In-Vivo Test on Trichostrongylus colubriformis and Haemonchuscontortus on Mongolian Gerbils (Meriones unquiculatus) Using PeroralApplication

Six to eight week old Mongolian gerbils are infected by artificialfeeding with ca. 2000 third instar larvae each of T. colubriformis andH. contortus. 6 days after infection, the gerbils are lightlyanaesthetised with N₂O and treated by peroral application with the testcompounds, dissolved in a mixture of 2 parts DMSO and 1 partpolyethylene glycol (PEG 300), in quantities of 100, 32 and 10 —0.1mg/kg. On day 9 (3 days after treatment), when most of the H. contortusthat are still present are late 4th instar larvae and most of the T.colubriformis are immature adults, the gerbils are killed in order tocount the worms. The efficacy is calculated as the % reduction of thenumber of worms in each gerbil, compared with the geometric average ofnumber of worms from 8 infected and untreated gerbils.

In this test, a vast reduction in nematode infestation is achieved withcompounds of formula I, especially from Table 1.

To examine the insecticidal and/or acaricidal activity of the compoundsof formula I on animals and plants, the following test methods may beused.

2. Activity On L₁ Larvae of Lucilia sericata

1 ml of an aqueous suspension of the active substance to be tested isadmixed with 3 ml of a special larvae growth medium at ca. 50° C., sothat a homogenate of either 250 or 125 ppm of active ingredient contentis obtained. Ca. 30 Lucilia larvae (L₁) are used in each test tubesample. After 4 days, the mortality rate is determined.

3. Acaricidal Activity On Boophilus microplus (Biarra strain)

A piece of sticky tape is attached horizontally to a PVC sheet, so that10 fully engorged female ticks of Boophilus microplus (Biarra strain)can be adhered thereto by their backs, side by side, in a row. Using aninjection needle, 1 μl of a liquid is injected into each tick. Theliquid is a 1:1 mixture of polyethylene glycol and acetone and itcontains, dissolved therein, a certain amount of active ingredientchosen from 1, 0.1 or 0.01 μg per tick. Control animals are given aninjection without active ingredient. After treatment, the animals arekept under normal conditions in an insectarium at ca. 28° C. and at 80%relative humidity until oviposition takes place and the larvae havehatched from the eggs of the control animals. The activity of a testedsubstance is determined by IR₉₀, i.e. an evaluation is made of thedosage of active ingredient at which 9 out of 10 female ticks (=90%) layeggs that are infertile even after 30 days.

4. In Vitro Efficacy On Engorged Female Boophilus microolus (BIARRA):

4×10 engorged female ticks of the OP-resistant BIARRA strain are adheredto a sticky strip and covered for 1 hour with a cotton-wool ball soakedin an emulsion or suspension of the test compound in concentrations of500, 125, 31 and 8 ppm respectively. Evaluation takes place 28 dayslater based on mortality, oviposition and hatched larvae.

An indication of the activity of the test compounds is shown by thenumber of females that

-   -   die quickly before laying eggs,    -   survive for some time without laying eggs,    -   lay eggs in which no embryos are formed,    -   lay eggs in which embryos form, from which no larvae hatch, and    -   lay eggs in which embryos form, from which larvae normally hatch        within 26 to 27 days.        5. In Vitro Efficacy On Nymphs of Amblyomma hebraeum

About 5 fasting nymphs are placed in a polystyrene test tube containing2 ml of the test compound in solution, suspension or emulsion.

After immersion for 10 minutes, and shaking for 2×10 seconds on a vortexmixer, the test tubes are blocked up with a tight wad of cotton wool androtated. As soon as all the liquid has been soaked up by the cotton woolball, it is pushed half-way into the test tube which is still beingrotated, so that most of the liquid is squeezed out of the cotton-woolball and flows into a Petri dish below.

The test tubes are then kept at room temperature in a room with daylightuntil evaluated. After 14 days, the test tubes are immersed in a beakerof boiling water. If the ticks begin to move in reaction to the heat,the test substance is inactive at the tested concentration, otherwisethe ticks are regarded as dead and the test substances regarded asactive at the tested concentration. All substances are tested in aconcentration range of 0.1 to 100 ppm.

6. Activity Against Dermanyssus galinae

2 to 3 ml of a solution containing 10 ppm active ingredient, and ca. 200mites (Dermanyssus gallinae) at different stages of development areadded to a glass container which is open at the top. Then the containeris closed with a wad of cotton wool, shaken for 10 minutes until themites are completely wet, and then inverted briefly so that theremaining test solution can be absorbed by the cotton wool. After 3days, the mortality of the mites is determined by counting the deadindividuals and indicated as a percentage.

7. Activity Against Musca domestica

A sugar cube is treated with a solution of the test substance in such away that the concentration of test substance in the sugar, after dryingover night, is 250 ppm. The cube treated in this way is placed on analuminium dish with wet cotton wool and 10 adult Musca domestica of anOP-resistant strain, covered with a beaker and incubated at 25° C. Themortality rate is determined after 24 hours.

1. A compound of formula I

wherein R₁ signifies halogen, cyano, nitro, C₁–C₂-alkyl,halo-C₁–C₂-alkyl, C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy or unsubstituted orsubstituted phenoxy, whereby the substituents may be independent of oneanother and are selected from the group consisting of halogen,C₁–C₄-alkyl, halo-C₁–C₄-alkyl, C₁–C₄-alkoxy and halo-C₁–C₄-alkoxy; R₃,R₄ and R_(5,) independently of one another, signify hydrogen, halogen,C₁–C₂-alkyl, halo-C₁–C₂-alkyl, or C₃–C₈-cycloalkyl; R₆ signifieshydrogen, C₁–C₂-alkyl, C₁–C₂-alkylcarbonal or benzyl; R₇ signifiesphenyl which is unsubstituted or substituted once or many times, wherebythe substituents may be independent of one another and are selected fromthe group consisting of halogen, nitro, cyano, C₁–C₂-alkyl,halo-C₁–C₂-alkyl, C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy, C₃–C₅-cycloalkyl,C₁–C₂-alkylthio, halo-C₁–C₂-alkylthio, C₁–C₂-alkylsulfonyl,halo-C₁–C₂-alkylsulfonyl, C₁–C₂-alkylcarbonyl, halo-C₁–C₂-alkylcarbonyl,C₁–C₂-alkoxycarbonyl; aryl-C₁–C₂-alkyl, which is unsubstituted orsubstituted once or many times, aryloxy which is unsubstituted orsubstituted once or many times, aryloxy-C₁–C₂-alkyl which isunsubstituted or substituted once or many times, and pyridyloxy which isunsubstituted or substituted once or many times, whereby thesubstituents may be independent of one another and are selected from thegroup consisting of halogen, nitro, cyano, C₁–C₂-alkyl,halo-C₁–C₂-alkyl, C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy, C₁–C₂-alkylthio,halo-C₁–C₂-alkylthio, C₁–C₂-alkylsulfonyl and halo-C₁–C₂-alkylsulfonyl;or hetaryl which is unsubstituted or substituted once or many times,whereby the substituents may be independent of one another and areselected from the group consisting of halogen, riltro, cyano,C₁–C₂-alkyl, halo-C₁–C₂-alkyl, C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy,C₂–C₄-alkenyloxy, halo-C₂–C₄-alkenyloxy, C₁–C₂-alkylthio,halo-C₁–C₂-alkylthio, C₁–C₂-alkylsulfonyl, halo-C₁–C₂-alkylsulfonyl; R₈and R₉, independently of one another, signify hydrogen or C₁–C₄-alkyl; Ysignifies C(O); a signifies 1: and m is 1 or
 2. 2. A compound of formulaI according to claim 1, wherein R₁ signifies halogen, cyano, nitro,C₁–C₂-alkyl, halo-C₁–C₂-alkyl, C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy; R₃, R₄and R₅, independently of one another, signify hydrogen, methyl orhalomethyl; R₅ signifies hydrogen or C₁–C₂-alkyl; R₇ signifies phenylwhich is unsubstituted or substituted once or many times, whereby thesubstituents may be independent of one another and are selected from thegroup consisting of halogen, cyano, C₁–C₂-alkyl, halo-C₁–C₂-alkyl,C₁–C₂-alkoxy, halo-C₁–C₂-alkoxy, C₃–C₅-cycloalkyl, C₁–C₂-alkylcarbonyl,halo-C₁–C₂-alkylcarbonyl, C₁–C₂-alkoxycarbonyl; aryl-C₁–C₂-alkyl whichis unsubstituted or substituted once or many times, andaryloxy-C₁–C₂-alkyl which is unsubstituted or substituted once or manylimes, whereby the substituents may each be independent of one anotherand are selected from the group consisting of halogen, cyano,C₁–C₂-alkyl, halo-C₁–C₂-alkyl, C₁–C₂-alkoxy and halo-C₁–C₂-alkoxy; R₅and R₉, independently of one another, signify hydrogen or C₁–C₂-alkyl; Ysignifies C(O); a signifies 1; and m is 1 or
 2. 3. A compound of formulaI according to claim 1 by nameN-[1-cyano-1-methyl-2-(5-chlorobenzotriazol-1-yl)-ethyl]-4-trifluoromethoxybenzamide.4. A method for the preparation of compounds of formula I, respectivelyin free form or in salt form, according to claim 1, whereby a compoundof formula II

which is known or may be produced analogously to corresponding knowncompounds, and wherein R₁, R₃, R₄, R₅, R₆, a and m are defined as givenfor formula I, is reacted with a compound of fomiula IIIQ—Y—R₇  III, which is known or may be prepared analogously tocorresponding known compounds, and wherein Y and R₇ are defined as givenfor formula I and Q is a leaving gfoup, optionally in the presence of abasic catalyst, and if desired, a compound of formula I obtainableaccording to the method or in another way, respectively in free form orin salt form, is converted into another compound of formula I, a mixtureof isomers obtainable according to the method is separated and thedesired isomer isolated andlor a free compound of formula I obtainableaccording to the method is converted into a salt or a salt of a compoundof formula I obtainable according to the method is converted into thefree compound of formula I or into another salt.
 5. A method for thepreparation of compounds of formula II, respectively in free form or insalt form, according to claim 4, whereby a compound of formula IV

which is known or may be produced analogously to corresponding knowncompounds, in which R₁, R₃, R₄, R₅, a and m are defined as for formulaI, is reacted with an inorganic or organic cyanide and a compound offormula R₆—NH₂, which is known or may be produced analogously tocorresponding known compounds and wherein R₆ is defined as for formulaI, and if desired, a compound of formula II obtainable according to themethod or in another way, respectively in free form or in salt form, isconverted into another compound of formula II, a mixture of isomersobtainable according to the method is separated and the desired isomerisolated and/or a free compound of formula II obtainable according tothe method is converted into a salt or a salt of a compound of formulaII obtainable according to the method is converted into the freecompound of formula II or into another salt.
 6. A composition whichcontains as active ingredient at least one compound of formula Iaccording to claim 1, in addition to carriers and/or dispersants.